Production method of copolymer of allyl monomer containing polar group

ABSTRACT

The present invention relates to a method for producing a high-molecular-weight copolymer of polar group-containing allyl monomers including monomer units represented by formulae (3) and (4) (in the formulae, R 1  represents a hydrogen atom (H) or hydrocarbon group having 1 to 6 carbon atoms; R 2  represents —OH, —OCOR 3  (R 3  represents hydrocarbon group having 1 to 5 carbon atoms), —N(R 4 ) 2  (R 4  represents a hydrogen atom or hydrocarbon group having 1 to 5 carbon atoms); and n and m are a value representing the molar ratio of each of the monomer units), which has few branches and unsaturated group at the molecular end, by copolymerizing olefin and an allyl compound using a metal complex of group 10 elements in the periodic system represented by formula (I) as a catalyst

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional of application Ser. No. 13/382,435filed Jan. 5, 2012, which is a National Stage of InternationalApplication No. PCT/JP2010/064980 filed Aug. 26, 2010, which claimsbenefit of Japanese Patent Application No. 2009-198533 filed Aug. 28,2009. The contents of application Ser. No. 13/382,435 are incorporatedherein by reference in their entirety.

TECHNICAL FIELD

The present invention relates to a production method of copolymers ofallyl monomer containing polar group and to the copolymers obtained bythe method.

BACKGROUND ART

Copolymers of olefin such as ethylene and propylene which is a nonpolarmonomer and a vinyl monomer containing polar group have been widelyknown. Specifically, ethylene-vinyl alcohol copolymers (EVOH) are randomcopolymer comprising ethylene and vinyl alcohol and synthesized bysaponifying ethylene-vinyl acetate copolymers obtained by radicalcopolymerization of ethylene and vinyl acetate. EVOH is used in a widerange of fields for purposes such as food packages by taking advantageof its excellent gas barrier property.

It is widely known that copolymers obtained by copolymerization ofethylene through radical polymerization generate short-chain branchesand long-chain branches by back biting reaction. For example, in thecase of EVOH, it has been reported that about 1 mol % of alkyl branchesand about 0.1 to 0.2 mol % of acetoxyl branches are present in EVOHcontaining about 30 mol % of ethylene (Nihon Kagaku Gakkaisi, 11, 1698(1977)). It is known that generally, presence of branches in the polymerchain incurs decrease in the degree of crystallization and changes inthe properties of the polymer.

The polymerization of monomers containing allyl group is more difficultcompared to that of vinyl monomers, and the polymer of allylgroup-containing monomers has been almost unheard. The main reason forthis is that the polymer propagation reaction proceeds very slowly dueto the degenerative chain transfer reaction to monomer and hence onlyoligomers having low degree of polymerization have been obtained (Chem.Rev. 58, 808 (1958)).

JP-A-S58-49792 discloses a copolymer of ethylene and allyl acetate and atripolymer of ethylene, allyl acetate and vinyl acetate as a hydrocarbonoil composition. The synthesizing method thereof is radicalpolymerization, and a low-molecular-weight substance having limitingviscosity of about 0.12 dl/g was obtained in Examples.

JP-A-2005-514083 discloses synthesis of ethylene-allyl alcohol copolymeraiming for higher hydrophobicity compared to EVOH as a coating materialfor medical instruments. The synthesis method is different from that ofthe present invention, which aims to directly obtain polymers bypolymerization of allyl monomers, and the targeted polymer is obtainedin JP-A-2005-514083 by reduction reaction after the radicalcopolymerization of ethylene and acrylic acid. However, the method had aproblem that the reduction reaction of the polymer cost too much.Furthermore, since the polymer is synthesized by radical polymerization,the polymer skeleton is presumed to have a branched structure.

Copolymerization of polar group-containing monomer by coordinationpolymerization using a Ziegler-Natta catalyst and a metallocene catalystis difficult to conduct under general conditions since the polar groupbecomes a catalyst poison, which is different from radicalpolymerization. U.S. Pat. No. 4,423,196 (Patent Document 1) disclosescopolymers of propylene and allyl alcohol which are obtained bypolymerization using TiCl₃-type Ziegler-Natta catalyst. Thepolymerization reaction proceeds by using equimolar organic aluminumcompound to allyl alcohol and by protecting the alcohol moiety withorganic aluminum. Though the publication does not have descriptionregarding the molecular weight distribution, the polymer contains 98% ofisotactic fraction and is presumed to be a polymer having a wide-rangeof molecular weight distribution and composition distribution.

Polymerization of nonpolar vinyl monomer such as ethylene and propyleneand polar monomer has also been attempted using single-site catalystswhich have been developed recent years.

It has been conventionally known that the catalyst using metal complexof group 4 elements has high polymerization activity to monomers such asethylene and propylene and there has also been a disclosure ofcopolymerization of polar group-containing monomers. In thecopolymerization of ethylene and polar group-containing monomer using ametallocene catalyst of group 4 elements, it was necessary to useorganic aluminum in at least an equimolar amount to allyl alcohol, whichaluminum functions as a protecting group for the polar group-containingmonomer against the catalyst. As a result, the reaction of chaintransfer to organic aluminum dominantly terminated the propagationreaction, and only a saturated terminal bond was observed in a terminalstructure of the polymer while a terminal double bond by β-hydrogenelimination was not. In this case, it leads to cost increases due to theuse of organic aluminum in excess; the fact that the copolymerization ofthe polar group-containing monomers cannot be high by the factor thatthe concentration of polar group-containing monomers cannot beincreased; and cost increases in recovering unreacted monomers after thepolymerization reaction, which become problems in achieving practicaluse of the method.

JP-A-2003-252930 (Patent Document 2) and J. Am Chem. Soc., 124, 1176(2002) (Non-patent Document 1) disclose an olefin polymer containing twopolar groups at position of ω of the main chain of the olefin polymerusing metallocene complex of group 4 elements having a specificstructure; an olefin polymer containing a polar group at position of ωand at least one position of (ω-n) (n≧1); and a production methodthereof. By the analysis of the terminal structure of the polymer, ithas been confirmed that only a saturated bond exists at the molecularchain terminal while an unsaturated bond does not. The allyl alcoholcontent in the polyethylene main chain of the copolymer obtained bycopolymerization of ethylene and allyl alcohol using a zirconocenecatalyst having a specific structure, which copolymer described inExamples, is within the range of from 0.2 to 1.2 mol %. Also, organicaluminum is used in at least an equimolar amount to allyl alcohol.

JP-A-2006-265541 (Patent Document 3) describes a method for producing apolar olefin copolymer using a metal complex of groups 4 to 5 elementshaving a specific structure. Examples disclose copolymerization ofethylene and allyl chloride, ethylene and allyl acetate, and ethyleneand allyl alcohol. In the copolymerization of ethylene and allylchloride, the allyl content in the main chain of polyethylene is from0.1 to 0.3 mol %; and organic aluminum is used in at least an equimolaramount to an allyl compound.

JP-A-2003-231710 (Patent Document 4) discloses a method for producing acopolymer of olefin and a polar vinyl monomer using a catalystcomprising a lamellar compound. Examples describe copolymerization ofpropylene and allyl alcohol, wherein the allyl alcohol content in thepolymer is as small as 0.3% or less and organic aluminum is used.

It is generally known that the polar group-containing monomer can becopolymerized without using organic aluminum as a protective group inthe catalyst system using late transition metal. Examples includecopolymerization of ethylene and acrylic acid ester, acrylonitrile,vinyl acetate and the like (J. Am. Chem. Soc., 118, 267 (1996)(Non-patent Document 2); J. Am. Chem. Soc., 129, 8948 (2007) (Non-patentDocument 3; JP-A-2007-046032 (Patent Document 5)). However,conventionally, not only that activity is low but that polymerizationactivity reduces during the long time period of polymerization in thecatalyst system using late transition metal, and therefore the cost ofcatalyst using expensive late transition metal complex is quite high andthe method has a problem to be industrially used.

On the other hand, in the case of allyl compound, the copolymerizationreaction of an allyl compound and olefin, which is an objective of thepresent invention, has been almost unheard because the reaction couldproceed in a different format other than the polymerization reaction atolefin moiety: i.e. an oxidative addition reaction of an allyl compoundto late transition metal.

PRIOR ART Patent Document

-   [Patent Document 1] U.S. Pat. No. 4,423,196-   [Patent Document 2] JP-A-2003-252930-   [Patent Document 3] JP-A-2006-265541-   [Patent Document 4] JP-A-2003-231710-   [Patent Document 5] JP-A-2007-46032

Non-Patent Document

-   [Non-patent Document 1] J. Am. Chem. Soc., 124, 1176 (2002)-   [Non-patent Document 2] J. Am. Chem. Soc., 118, 267 (1996)-   [Non-patent Document 3] J. Am. Chem. Soc., 129, 8948 (2007)

SUMMARY OF THE INVENTION Problems to be Solved by the Invention

An objective of the present invention is to provide a high molecularweight allyl copolymer containing polar group and having a novelstructure, which copolymer is available for various applications and thesynthesis thereof has been considered to be difficult by apolymerization method such as radical polymerization other than that ofthe present invention; and a production method thereof.

Means to Solve the Problem

As a result of intensive studies to solve the above-mentioned problem,the present inventors have found that a novel copolymer of the allylmonomer containing a polar group, which copolymer has a novel structureand is available for various applications, can be provided bypolymerizing polar group-containing allyl monomer using a metal complexof group 10 elements as a catalyst component, which is different fromthe conventional radical polymerization method and the method using anearly transition metal catalyst. The present inventors accomplished thepresent invention based on this finding.

That is, the present invention relates to the following [1] to [15]:

[1] A method for producing a copolymer of polar group-containing allylmonomers having monomer units represented by formulae (3) and (4)

(in the formulae, R¹ represents a hydrogen atom or hydrocarbon grouphaving 1 to 6 carbon atoms;R² represents —OH, —OCOR³ (R³ represents hydrocarbon group having 1 to 5carbon atoms), —N(R⁴)₂ (R⁴ represents a hydrogen atom, hydrocarbon grouphaving 1 to 5 carbon atoms, aromatic residue having 6 to 18 carbon atomsor —COOR¹⁰ (R¹⁰ represents hydrocarbon group having 1 to 10 carbon atomsor aromatic residue having 6 to 10 carbon atoms) and two R⁴s may be thesame or different from each other) or a halogen atom; and n and m are avalue representing the molar ratio of each of the monomer units),comprising copolymerization of olefin represented by formula (1)

CH₂═CHR¹  (1)

(in the formula, R¹ has the same meaning as described above) and anallyl compound represented by formula (2)

CH₂═CHCH₂R²  (2)

(in the formula, R² has the same meaning as described above) using as acatalyst a metal complex represented by formula (C1)

(in the formula, M represents a metal atom of group 10 element in theperiodic system; X represents a phosphorous atom (P) or an arsenic atom(As); R⁵ represents a hydrogen atom or hydrocarbon group having 1 to 30carbon atoms which may be substituted by one or more groups selectedfrom a halogen atom, alkoxy group, aryloxy group and acyloxy group; Y,R⁶ and R⁷ independently represent a hydrogen atom, alkoxy group, aryloxygroup, silyl group, amino group or hydrocarbon group having 1 to 30carbon atoms which may be substituted by one or more groups selectedfrom a halogen atom, alkoxy group and aryloxy group; and R⁶ and R⁷ maybond to each other to form a ring structure. Q represents a bivalentgroup indicated in the brackets of Z[—S(═O)₂—O-]M, Z[—C(═O)—O-]M,Z[—P(═O) (—OH)—O-]M orZ[—S-]M (Z and M at the beginning and at the end of the formulae aredescribed to show the coupling direction of the groups). Z represents ahydrogen atom or a hydrocarbon group having 1 to 40 carbon atoms whichmay be substituted by one or more groups selected from a halogen atom,alkoxy group and aryloxy group. Y and Z may bond to each other to form aring structure. R⁶ and/or R⁷ may bond to Y to form a ring structure. Lrepresents an electron-donating ligand and q is 0, ½, 1 or 2).[2] The method for producing a copolymer as described in [1] above,wherein the catalyst represented by formula (C1) is represented byformula (C2)

(in the formula, Y¹ represents bivalent hydrocarbon group having 1 to 70carbon atoms which may be substituted by one or more groups selectedfrom a halogen atom, alkoxy group and aryloxy group; Q, M, X, R⁵, R⁶,R⁷, L and q have the same meanings as in [1] above).[3] The method for producing a copolymer as described in [2] above,wherein Q in formula (C2) is —SO₂—O— (in which S bonds to Y¹ and O bondsto M).[4] The method for producing a copolymer as described in [3] above,wherein the catalyst represented by formula (C2) is represented byformula (C3)

(in the formula, four R⁸s independently represent a hydrogen atom, alkylgroup having 1 to 8 carbon atoms, alkoxy group having 1 to 8 carbonatoms, aryloxy group having 6 to 18 carbon atoms or a halogen atom; andM, R⁵, R⁶, R⁷, L and q have the same meanings as in [1] above).[5] The method for producing a copolymer as described in [4] above,wherein both of R⁶ and R⁷ in formula (C3) represent cyclohexyl group,cyclopentyl group, isopropyl group, o-methoxyphenyl group,2′,6′-dimethoxy-2-biphenyl group; and all of R⁸s are a hydrogen atom orone of R⁸s is ethyl group while the other three R⁸s are a hydrogenatom).[6] The method for producing a copolymer as described in any one of [1]to [5] above, wherein M is Pd.[7] The method for producing a copolymer as described in any one of [1]to [3] above, wherein X is P.[8] A copolymer of polar group-containing allyl monomers obtained by aproduction method as described in any one of [1] to [7] above.[9] A copolymer of polar group-containing allyl monomers, which is acopolymer containing monomer units represented by formulae (3-1) and (4)

(in the formulae, R¹⁻¹ represents a hydrogen atom or methyl group andR², n and m have the same meaning as in [1] above); (A) the main chainhas one or less branch, which has two or more carbon atoms, per 1000carbon atoms which constitute the main chain; and (B) the main chain hasa carbon-to-carbon double bond at least at one end of the main chain.[10] The copolymer of polar group-containing allyl monomers as describedin [9] above which further has a structure that:(C) the number average molecular weight in terms of polystyrene (Mn) is1,000 or more and 1,000,000 or less;(D) the molecular weight distribution (Mw/Mn) is 1.0 or more and 3.0 orless; and(E) n and m representing the molar ratio of the monomer unitsrepresented by formulae (3-1) and (4) satisfy the following formula:

0.1≦{m/(m+n)}×100≦50

[11] The copolymer of polar group-containing allyl monomers as describedin [9] or [10] above, which contains only the monomer units representedby formulae (3-1) and (4).[12] The copolymer of polar group-containing allyl monomers as describedin [9] or [10] above, which contains monomer units represented byformulae (3-1), (4-1) and (4-2)

(in the formula, R¹⁻¹ has the same meaning as described above; and n, m₁and m₂ represent the molar ratio of each of the monomer units).[13] The copolymer of polar group-containing allyl monomers as describedin any one of [9] to [11] above, wherein R¹⁻¹ in formula (3-1) is ahydrogen atom.[14] The copolymer of polar group-containing allyl monomers as describedin any one of [9] to [11] above, wherein the monomer unit represented byformula (4) is derived from at least one allyl compound selected fromallyl acetate, allyl chloride, allyl bromide, allyl amine,N-allylaniline and N-t-butoxycarbonyl-N-allylamine.[15] The copolymer of polar group-containing allyl monomers as describedin any one of [9] to [11] above, wherein R¹⁻¹ in formula (3-1) is ahydrogen atom and the monomer unit represented by formula (4) is derivedfrom at least one allyl compound selected from allyl acetate, allylchloride, allyl bromide, allyl amine, N-allylaniline andN-t-butoxycarbonyl-N-allylamine.

Effects of the Invention

A high molecular weight copolymer of allyl monomers containing a polargroup can be obtained by the method of the present invention, whereinthe polar group-containing allyl monomer and olefin are copolymerizedusing a metal complex of group 10 elements as a catalyst component,which copolymer was difficult to obtain by a conventional method.Particularly, the polymer containing structures of (A) and (B) describedbelow can be directly obtained using the allyl polar group as one of thecopolymerizable monomers.

That is, the polar group-containing allyl copolymer of the presentinvention contains:

(A) not a structure containing branches obtained by the conventionalradical polymerization but a structure wherein the polymethylenestructure in the main chain has a linear structure. This structureenables high crystallinity, thereby attaining various properties such asexcellent mechanical strength; and(B) a double bond in the terminal structure of the polymer. The use ofthe terminal double bond enables necessary modification of a functionalgroup, block copolymerization and star polymers.

Furthermore, though the present invention uses expensive late transitionmetal complex as a main component, it enables greatly reducing thecatalyst cost by improving activity and dramatically improving thecatalyst lifetime.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 The ¹³C-NMR spectrum of the ethylene/allyl acetate copolymerobtained in Example 1

FIG. 2 An enlarged view of the portion at 12 to 40 ppm of FIG. 1

FIG. 3 A figure showing a terminal structure, a chemical shift of the¹³C-NMR spectrum, and the carbon identification in the alphabet in thepolymer analysis of Example 1

FIG. 4 The IR spectrum of the ethylene/allyl acetate copolymer obtainedin Example 1

FIG. 5 The IR spectrum of the ethylene/allyl alcohol copolymer obtainedin Example 36

FIG. 6 The ¹³C-NMR spectrum of the ethylene/allyl chloride copolymerobtained in Example 41

FIG. 7 An enlarged view of the portion at 10 to 55 ppm of FIG. 6

FIG. 8 A figure showing a terminal structure, a chemical shift of the¹³C-NMR spectrum, and the carbon identification in the alphabet in thepolymer analysis of Example 41

FIG. 9 The ¹³C-NMR spectrum of the ethylene/allyl bromide copolymerobtained in Example 44

FIG. 10 An enlarged view of the portion at 10 to 45 ppm of FIG. 9

FIG. 11 A figure showing a terminal structure, a chemical shift of the¹³C-NMR spectrum, and the carbon identification in the alphabet in thepolymer analysis of Example 44

FIG. 12 The ¹³C-NMR spectrum of the ethylene/N-allylaniline copolymerobtained in Example 46

FIG. 13 An enlarged view of the portion at 10 to 55 ppm of FIG. 12

FIG. 14 An enlarged view of the portion at 105 to 155 ppm of FIG. 12

FIG. 15 A figure showing a terminal structure, a chemical shift of the¹³C-NMR spectrum, and the carbon identification in the alphabet in thepolymer analysis of Example 46

FIG. 16 A graph indicating the relationship between the polymerizationtime and the polymer productivity per catalyst in Examples 32 to 35

EMBODIMENT TO CARRY OUT THE INVENTION [Monomer]

Olefin, which is one of the monomers used in the method for producingthe copolymer of the present invention, is represented by formula (1).

CH₂═CHR¹  (1)

In formula (1), R¹ represents a hydrogen atom or hydrocarbon grouphaving 1 to 6 carbon atoms and is preferably a hydrogen atom or alkylgroup having 1 to 3 carbon atoms. Specifically, examples of olefin offormula (1) include ethylene, propylene, 1-butene, 1-hexene,4-methyl-1-pentene and 1-octene. Among these, ethylene and propylene areparticularly preferable. One of these compounds may be usedindependently or two or more of them may be used in combination.

A polar group-containing allyl compound, which is the other of themonomers used for polymerization in the present invention, isrepresented by formula (2).

CH₂═CHCHR²  (2)

In formula (2), R² represents —OH, —OCOR³ (R³ represents hydrocarbongroup having 1 to 5 carbon atoms), —N(R⁴)₂ (R⁴ represents a hydrogenatom, hydrocarbon group having 1 to 5 carbon atoms or aromatic residuehaving 6 to 18 carbon atoms or —COOR¹⁰ (R¹⁰ represents hydrocarbon grouphaving 1 to 10 carbon atoms or aromatic residue having 6 to 10 carbonatoms), wherein two R⁴s may by the same or different) or a halogen atom.R³ is preferably alkyl group having 1 to 3 carbon atoms, particularlymethyl group. R⁴ is preferably a hydrogen atom, alkyl group having 1 to3 carbon atoms or phenyl group. R¹⁰ of —COOR¹⁰ is preferably linear orbranched alkyl group having 1 to 4 carbon atoms, phenyl group, benzylgroup and the like. The halogen atom of R² is preferably chlorine orbromine.

Specific examples of the polar group-containing allyl compoundrepresented by formula (2) include allyl acetate, allyl alcohol, allylamine, N-allylaniline, N-t-butoxycarbonyl-N-allylamine,N-benzyloxycarbonyl-N-allylamine, N-benzyl-N-allylamine, allyl chlorideand allyl bromide. Among these, allyl acetate and allyl alcohol areparticularly preferable. One of these compounds may be usedindependently or two or more of them may be used in combination.

In addition to the compounds (monomers) represented by formulae (1) and(2), the other monomer may be incorporated to be copolymerized. Theother monomers include acrylate ester, metacrylate ester, acrylonitrile,vinyl acetate and styrene.

Examples of the combination of olefin represented by formula (1) and theallyl compound represented by formula (2) include ethylene and allylacetate; ethylene and ally alcohol; ethylene, allyl acetate and allylalcohol; ethylene and allyl chloride; ethylene and allyl bromide;ethylene and allylamine, ethylene and N-allylaniline; ethylene andN-t-butoxycarbonyl-N-allylamine; ethylene andN-benzyloxycarbonyl-N-allylamine; ethylene and N-benzyl-N-allylamine;propylene and allyl acetate; propylene and ally alcohol; propylene,allyl acetate and allyl alcohol; propylene and allyl chloride; propyleneand allyl bromide; propylene and allylamine; propylene andN-allylaniline; propylene and N-t-butoxycarbonyl-N-allylamine; propyleneand N-benzyloxycarbonyl-N-allylamine; and propylene andN-benzyl-N-allylamine. Among these, preferred are ethylene and allylacetate; ethylene and allyl alcohol; ethylene, allyl acetate and allylalcohol; ethylene and allyl chloride; and ethylene and allylamine fromthe viewpoint of the polymer performance and economic efficiency.

[Catalyst]

The (structure of the) catalyst comprising metal complex of group 10elements of the periodic system used in the present invention isrepresented by formula (C1).

In the formula, M represents a metal atom of group 10 elements in theperiodic system. X represents a phosphorous (P) atom or an arsenic (As)atom. R⁵ represents a hydrogen atom or a hydrocarbon group having 1 to30 carbon atoms which may be substituted by one or more groups selectedfrom a halogen atom, alkoxy group and aryloxy group. Y, R⁶ and R⁷independently represent a hydrogen atom, alkoxy group, aryloxy group,silyl group, amino group, or a hydrocarbon group having 1 to 30 carbonatoms which may be substituted by one or more groups selected from ahalogen atom, alkoxy group and aryloxy group. R⁶ and R⁷ may bond to eachother to form a ring structure. Q represents a bivalent group indicatedin the brackets of Z[—S(═O)₂—O-]M, Z[—C(═O)—O-]M, Z[—P(═O)(—OH)—O-]M or

Z[—S-]M (Z and M at the beginning and at the end of the formulae aredescribed to show the coupling direction of the groups). Z represents ahydrogen atom or a hydrocarbon group having 1 to 40 carbon atoms whichmay be substituted by one or more groups selected from a halogen atom,alkoxy group and aryloxy group. Y and Z may bond to each other to form aring structure. R⁶ and/or R⁷ may bond to Y to form a ring structure. Lrepresents an electron-donating ligand and q is 0, ½, 1 or 2. In thepresent specification, a “hydrocarbon group” includessaturated/unsaturated aliphatic carbon group and aromatic hydrocarbongroup.

The structure of formula (C1) is described below.

M represents an element of group 10 in the periodic system. The elementsof group 10 in the periodic system include Ni, Pd and Pt. From theviewpoint of the catalytic activity and obtained molecular weight, Niand Pd are preferable, and Pd is particularly preferable.

X represents a phosphorous (P) atom or an arsenic (As) atom, wherein twoelectrons coordinate to M. P is preferred as X for reasons ofavailability and the catalyst cost.

Y, R⁶ and R⁷ each independently represent a hydrogen atom, alkoxy group,aryloxy group, silyl group, amino group, or a hydrocarbon group having 1to 30 carbon atoms which may be substituted by one or more groupsselected from a halogen atom, alkoxy group and aryloxy group. As thealkoxy group, preferred are those having 1 to 20 carbon atoms includingmethoxy group, ethoxy group, propoxy group and isopropoxy group. As thearyloxy group, preferred are those having 6 to 24 carbon atoms includingphenoxy group. Examples of the silyl group include trimethyl silylgroup, and examples of the amino group include amino group, methyl aminogroup and dimethyl amino group. R⁶ and R⁷ may be the same or differentfrom each other. Also, R⁶ and R⁷ may bond to each other to form a ringstructure. R⁶ and/or R⁷ may bond to Y to form a ring structure. Examplesof the hydrocarbon group having 1 to 30 carbon atoms which may besubstituted by one or more groups selected from a halogen atom, alkoxygroup and aryloxy group in Y, R⁶ and R⁷ include alkyl group, aryl group,cycloalkyl group and furyl group. Specific examples of the alkoxy groupand aryloxy group in the hydrocarbon group having 1 to 30 carbon atomswhich may be substituted by one or more groups selected from a halogenatom, alkoxy group and aryloxy group are the same as those mentionedabove. The halogen atom is preferably fluorine. From the viewpoint ofthe catalyst activity, alkyl group and aryl group are particularlypreferable.

Specific examples of Y—X—R⁶/R⁷ moiety in which X is a phosphorous (P)atom, that is,

include the structures in the following formulae. Here, the bond betweenP and M are not shown.

Specific examples of Y—X—R⁶/R⁷ moiety in which X is an arsenic (As)atom, that is,

include the structures in the following formulae:

R⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 30carbon atoms which may be substituted by one or more groups selectedfrom a halogen atom, alkoxy group, aryloxy group and acyloxy group. Apreferred hydrocarbon group having 1 to 30 carbon atoms which may besubstituted by one or more groups selected from a halogen atom, alkoxygroup and aryloxy group is alkyl group having 1 to 6 carbon atoms. Apreferred halogen atom is chloride and bromide. Preferred alkoxy groupis methoxy group and ethoxy group. Preferred aryloxy group is phenoxygroup. Preferred acyloxy group is acetoxy group and pivaloxy group.Particularly preferable examples of R⁵ include a hydrogen atom, methylgroup, ethyl group, n-propyl group, isopropyl group, methoxymethylgroup, phenoxy methyl group, 1-acetoxyphenyl group and 1-pivaloxypropylgroup.

Q represents a bivalent group indicated by —S(═O)₂—O—, —C(═O)—O—,—P(═O)(—OH)—O— or —S—, which is a moiety, wherein one electroncoordinates to M. The left side of each of the above-mentioned formulaebonds to Z while the right side bonds to M. Among these, —S(═O)₂—O— isparticularly preferable from the viewpoint of the catalyst activity.

Z represents a hydrogen atom or a hydrocarbon group having 1 to 40carbon atoms which may be substituted by one or more groups selectedfrom a halogen atom, alkoxy group and aryloxy group. Y and Z may bond toeach other to form a ring structure. Specific examples of the halogenatom, alkoxy group and aryloxy group in the “hydrocarbon atom having 1to 40 carbon atoms which may be substituted by one or more groupsselected from a halogen atom, alkoxy group and aryloxy group” includethose mentioned as the examples in Y, R⁶ and R⁷. Examples of hydrocarbonatom having 1 to 40 carbon atoms include methyl group, ethyl group,isopropyl group, t-butyl group, isobutyl group, cyclohexyl group,cyclopentyl group, phenyl group, 2-i-propylphenyl group, and2,6-di-i-propylphenyl group.

Z-Q moiety is an oxygen atom or a sulfur atom having highelectronegativity and one electron of the oxygen or sulfur atom of Z-Qmoiety coordinates to metal atom M. Since the bonding electron betweenZ-Q-M is transferred from M to Z-Q, Z-Q and M may be indicated formallyas an anion state and a cation state, respectively.

In formula (C1), Y moiety and Z moiety may bond to each other. In thiscase, formula (C1) can be represented by formula (C2). In formula (C2),Y—Z moiety as a whole is indicated by Y¹. Here, Y¹ represents across-linked structure between Q and X.

In the formula, Y¹ represents a bivalent hydrocarbon group having 1 to70 carbon atoms which may be substituted by one or more groups selectedfrom a halogen atom, alkoxy group and aryloxy group. Q, M, X, R⁵, R⁶,R⁷, L and q have the same meanings as in formula (C1).

Specific examples of a halogen atom, alkoxy group and aryloxy group asY¹ are the same as those as Y. Examples of the hydrocarbon group having1 to 70 carbon atoms include alkylene group and arylene group.Particularly preferred is arylene group.

Examples of [(R⁶)(R⁷)P] moiety when X is P (a phosphorous atom) includethe following structures. In the following structure formulae, the bondbetween P and M or Y¹ is not shown.

The cross-linked structure Y¹ is the crosslinking moiety which binds Xand Q moiety. Specific examples of the cross-linked structure Y¹ inwhich X is represented by a P atom are shown below. Here, multiple R⁹smay be the same or different to each other and represent a hydrogenatom, halogen atom, hydrocarbon group having 1 to 20 carbon atoms, or ahydrocarbon group having 1 to 20 carbon atoms substituted by a halogenatom.

Substituents R⁶ and R⁷ may bond to Y¹ moiety to form a ring structure.Specific examples include the structures as follows:

Among the catalysts represented by formula (C2), those represented bythe following formula (C3) are particularly preferable.

In the formula, four R⁸s independently represent a hydrogen atom, alkylgroup having 1 to 8 carbon atoms, alkoxy group having 1 to 8 carbonatoms, aryloxy group having 6 to 18 carbon atoms or halogen atom; and M,R⁵, R⁶, R⁷, L and q have the same meanings as those in formula (C1).

In formula (C3), preferred R⁵ is an alkyl group having 1 to 6 carbonatoms, particularly methyl group. Both of R⁶ and R⁷ are preferably acyclohexyl group, cyclopentyl group or isopropyl group. M is preferablyPd.

The metal complex of the catalysts represented by formulae (C1) and (C2)can be synthesized according to the known documents (for example, J. Am.Chem. Soc. 2007, 129, 8948). That is, a metal complex is synthesized byreacting zerovalent or bivalent M source with a ligand in formula (C1)or (C2).

The compound represented by formula (C3) can be synthesized by making Y¹and Q in formula (C2) a specific group corresponding to formula (C3).

Examples of zerovalent M source include tris(dibenzylidene acetone)dipalladium as a palladium source and tetracarbonyl nickel(0) (Ni(CO)₄)and bis(1,5-cyclooctadiene)nickel as a nickel source.

Examples of bivalent M source include(1,5-cyclooctadiene)(methyl)palladium chloride, palladium chloride,palladium acetate, bis(acetonitrile)dichloropalladium (PdCl₂(CH₃CN)₂),bis(benzonitrile)dichloropalladium (PdCl₂(PhCN)₂),(N,N,N′,N′-tetramethylethylenediamine)dichloro palladium(II)(PdCl₂(TMEDA)), (N,N,N′,N′-tetramethylethylenediamine)dimethyl palladium(II) (PdMe₂(TMEDA)), palladium(II) acetylacetonate (Pd(acac)₂),palladium(II) trifluoromethanesulfonate (Pd(OCOCF₃)₂) as a palladiumsource and (allyl)nickel chloride, (allyl)nickel bromide, nickelchloride, nickel acetate, nickel(II) acetylacetonate (Ni(acac)₂),(1,2-dimethoxyethane)dichloronickel(II) (NiCl₂(DME)) and nickel(II)trifluoromethanesulfonate (Ni(OSO₂CF₃)₂) as a nickel source.

While an isolated metal complex represented by formula (C1) or (C2) canbe used, the metal complex generated by bringing a M-containing metalsource and a ligand precursor in the reaction system can also be usedfor in-situ polymerization without isolating the metal complex.Particularly, when R⁵ in formulae (C1) and (C2) is a hydrogen atom, itis preferable to use the metal complex generated in situ after reactinga metal source containing zerovalent M and a ligand precursor forpolymerization without isolating the metal complex.

In this case, ligand precursors represented by formulae (C1-1) and(C1-2) can be used for a metal complex represented by formula (C1).

X—Y(R⁶)(R⁷)  (C1-1)

(Symbols in the formula have the same meanings as mentioned above.)

Z-Q-R⁵  (C1-2)

(Symbols in the formula have the same meanings as mentioned above.)

The ligand precursor represented by the following formula (C2-1) can beused for a metal complex represented by formula (C2).

(Symbols in the formula have the same meanings as mentioned above.)

In formula (C1), it is preferable to select the ratio between the Msource (M) and a ligand precursor (C1-1) (X) or a ligand precursor(C1-2) (Z) (i.e. X/M or Z/M) or the ratio between the M source (M) and aligand precursor (C2-1) (C2 ligand) (i.e. (C2 ligand)/M) within therange of from 0.5 to 2.0, more preferably from 1.0 to 1.5.

When isolating the metal complex of formula (C1) or (C2), the onestabilized by making an electron-donating ligand (L) coordinate to themetal complex in advance may be used. In this case, q is ½, 1 or 2. q of½ means that a bivalent electron-donating ligand coordinates to twometal complexes. q is preferably ½ or 1 to stabilize a metal complexcatalyst. q of 0 means that there is no ligand in the precursor.

An electron-donating ligand (L) is a compound which contains anelectron-donating group and is capable of stabilizing a metal complex bycoordinating to metal atom M.

As the electron-donating ligand (L), examples of those containing asulfur atom include dimethyl sulfoxide (DMSO). Examples of thosecontaining a nitrogen atom include trialkyl amine having 1 to 10 carbonatoms in alkyl group, dialkyl amine having 1 to 10 carbon atoms in alkylgroup, pyridine, 2,6-dimethylpyridine (otherwise known as “lutidine”),aniline, 2,6-dimethylaniline, 2,6-diisopropylaniline,N,N,N′,N′-tetramethylethylenediamine (TMEDA),4-(N,N-dimethylamino)pyridine (DMAP), acetonitrile and benzonitrile.Examples of those containing an oxygen atom include diethyl ether,tetrahydrofuran and 1,2-dimethoxyethane.

The metal complex represented by formula (C1) or (C2) may be supportedon a support to be used for polymerization. In this case, there are noparticular limitations on the support and examples include an inorganicsupport such as silica gel and alumina and an organic support such aspolystyrene, polyethylene and polypropylene. Examples of the method fordepositing a metal complex on a support include a physical adsorptionmethod of impregnating the support with a solution of the metal complexand drying it and a method of depositing the metal complex onto asupport by chemically bonding the metal complex to a support.

[Polymerization Method]

When the metal complex of the present invention is used as a catalyst,there are no particular limitations on the method of polymerizingmonomers represented formulae (1) and (2) and the monomers can bepolymerized by a widely-used method. That is, a process such as asolution polymerization method, a suspension polymerization method and agas-phase polymerization method is available. Particularly preferred area solution polymerization method and a suspension polymerization method.

A mixture of two or more of the metal complex catalysts represented byformula (C1), (C2) or (C3) may be used for the polymerization reaction.Using the catalysts in mixture enables controlling the molecular weightand molecular weight distribution of the polymer and the content of themonomer unit represented by formula (4) to thereby obtain a polymersuitable for the desired use. The molar ratio between the metal complexcatalyst represented by formula (C1), (C2) or (C3) and the total amountof monomers (monomers/metal complex) is within the range of from 1 to10,000,000, preferably the range of from 10 to 1,000,000, morepreferably the range of from 100 to 100,000.

There are no particular limitations on the polymerization temperature.The polymerization is generally conducted at a temperature in the rangeof from −30 to 200° C., preferably in the range of from 0 to 180° C.,more preferably in the range of from 20 to 150° C.

The polymerization is conducted at a polymerization pressure, whereinthe internal pressure consists mostly of the pressure of olefinrepresented by formula (1), in the range from normal pressure to 20 MPa,preferably in the range from normal pressure to 10 MPa.

The polymerization time can be appropriately adjusted depending on theprocessing mode and the polymerization activity of the catalyst, and canbe as short as several minutes or as long as several thousand hours.

It is preferable to fill the atmosphere in the polymerization systemwith an inert gas such as nitrogen and argon to prevent components otherthan monomers such as air, oxygen and moisture being mixed into theatmosphere to retain the catalyst activity. In the case of the solutionpolymerization, an inert solvent may be used in addition to monomers.There are no particular limitations on the inert solvent, and examplesinclude aliphatic hydrocarbon such as isobutane, pentane, hexane,heptane and cyclohexane; aromatic hydrocarbon such as benzene, tolueneand xylene; halogenated aliphatic hydrocarbon such as chloroform,methylene chloride, carbon tetrachloride, dichloroethane andtetrachloroethane; halogenated aromatic hydrocarbon such aschlorobenzene, dichlorobenzene and trichlorobenzene; aliphatic estersuch as methyl acetate and ethyl acetate; and aromatic ester such asmethyl benzoate and ethyl benzoate.

In addition to the compounds represented by formulae (1) and (2), one ormore types of third polymer units may be introduced into the copolymerof the polar group-containing allyl monomers of the present invention tothereby add functions to the polymer. Examples of the third monomerinclude an olefin compound having 9 or more carbon atoms and polargroup-containing monomer other than an allyl monomer. Examples of theolefin compound having 9 or more carbon atoms include 1-nonene and1-decene. Examples of a polar group-containing monomer other than anallyl monomer include acrylic acid, acrylic acid ester, metacrylic acid,metacrylic acid ester and acrylonitrile.

The polymer of the present invention can be converted into variouspolymers using the reactivity of the functional group. For example, whenR² is hydroxyl group, a graft polymer can be produced in which two ormore polymers are bonded to each other by substituting a primaryhydroxyl group by halogen as a starting point of living radicalpolymerization to polymerize various polar group-containing monomers byradical polymerization. Examples of radically polymerizable monomers inthis case include acrylic acid ester, metacrylic acid ester,acrylonitrile, vinyl acetate and styrene.

The blending ratio of the monomers represented by formulae (1) and (2)is to be appropriately adjusted depending on the composition ratio ofthe targeted copolymer. This includes a case where a third monomer isused.

The monomer represented by formula (1) is in the form of gas at apolymerization reaction temperature, the pressure of which is to becontrolled. The monomer represented by formula (2) can be used as it isor may be diluted with an inert solvent to adjust the monomer blendingratio.

After completion of the polymerization reaction, the copolymer as areaction product is to be isolated by post-treatment using a knownoperation and treating method (e.g. neutralization, extraction withsolvents, washing with water, liquid separation, distillation withsolvents and reprecipitation).

The copolymer can be molded into the form of a pellet, film, sheet andthe like under conditions for general thermoplastic resin.

The copolymer of allyl acetate with olefin such as ethylene can beconverted to an allyl alcohol copolymer by saponification. When thecopolymer is partially saponified, it becomes a tripolymer of ethylene,allyl alcohol and allyl acetate.

The obtained copolymer can be a product per se by molding such asinjection molding, extrusion and film processing. Or the copolymer maybe added to polyolefin and the like to be used as a modifier of thesurface features such as adhesiveness and printing performance; acompatibility agent between nonpolar polyolefin and highly-polar otherresins; and a dispersing agent of pigments and the like. The copolymermay also be used for purposes such as paint, ink, adhesive agent,binder, plasticizer, lubricant, lubricant oil and surface active agent.

[Copolymer of Polar Group-Containing Allyl Monomers]

The copolymer of polar group-containing allyl monomers of the presentinvention is obtained by polymerizing compounds represented by the aboveformulae (1) and (2) and a third monomer as needed in the presence ofthe above-mentioned catalyst. The copolymer of polar group-containingallyl monomers of the present invention is a copolymer containingmonomer units represented by formulae (3-1) and (4)

(in formulae, R¹⁻¹ represents a hydrogen atom or methyl group and R², nand m have the same meaning as mentioned above) and having structures asdescribed in (A) and (B) below:

-   (A) The main chain has one or less branch, which has two or more    carbon atoms, per 1000 carbon atoms which constitute the main chain.-   (B) The main chain has a carbon-to-carbon double bond at least at    one end of the main chain.    It is more preferable for the copolymer to satisfy the requirements    as stated in (C), (D) and (E) below:    (C) The number average molecular weight in terms of polystyrene (Mn)    is 1,000 or more and 1,000,000 or less    (D) The molecular weight distribution (Mw/Mn) is 1.0 or more and 3.0    or less    (E) The molar ratio of the monomer units represented by formulae    (3-1) and (4) (n and m) satisfies the following formula:

0.1≦{m/(m+n)}×100≦50

In formula (3-1), R¹⁻¹ represents a hydrogen atom or methyl group,preferably a hydrogen atom. R², m and n have the same meanings asmentioned above.

In the present invention, a branch means the one having two or morecarbon atoms and the side chain of the monomer is not to be counted as abranch.

As a polymer chain structure, a linear structure and a branchedstructure are generally known. It is known that a branched structure isobtained by back biting mechanism in ethylene-based polymers obtained byradical polymerization. In the branched structure, there existshort-chain branches having 5 or less carbon atoms and long-chainbranches starting from the radical generated in the main chain, whichare obtained by back biting. Meanwhile, the copolymer obtained by thecatalyst system of the present invention has a linear structurecontaining very few long-chain branches. The copolymer of the presentinvention has a branch of one or less per 1000 carbon atoms whichconstitute the main chain. Here, the number of branches per 1000 carbonatoms can be calculated by measuring the number of tertiary carbon atomsin the main chain to which a branch having two or more carbon atoms arebonded by the ¹³C-NMR spectrum. The side chains of the monomer are notcounted in the branches in the present invention. For example, when1-butene is copolymerized as a third monomer, ethyl group becomes a sidechain and shall not be counted as a branch.

The terminal structure of the polymer of the present invention isdifferent from that of the main chain. One may grasp the terminalstructure divided between the initiation end which arises at theinitiation of polymerization and the terminal end which arises at thetermination of polymerization. Since the initiation end is formed byinserting olefin in the bond between metal and a hydrogen atom orbetween metal and alkyl group, the end has a saturated bond structure.The terminal end structures are divided into a saturated bond and anunsaturated bond depending on the reaction mechanism. When a chaintransfer agent containing alkyl group such as organic aluminum is usedin the reaction system, the molecular chain transfers to aluminum atoms,which terminates the polymerization reaction and makes a terminalstructure have a saturated bond. When a titanium trichloride-basedZiegler-Natta catalyst and a metal complex of group 4 elements are usedas a catalyst, organic aluminum is used to copolymerize a polar-groupcontaining allyl compound, which makes a terminal structure have asaturated bond. On the other hand, since organic aluminum is not used inthe present invention, polymer chain growth terminates by β-hydrogenelimination, which makes at least one of the terminal structures has anunsaturated double bond.

In the formula, R means R¹ or CH₂R² in formula (1) or (2) and “Polymer”means a polymer chain.

An unsaturated double bond can be confirmed by analyzing the NMRspectrum of the copolymer. The terminal unsaturated bond is highlyreactive and enables modification of functional groups, blockcopolymerization and production of star polymers. Therefore, thecopolymer of the present invention is very useful.

Copolymers of the polar group-containing allyl monomers having a numberaverage molecular weight of 3,000 or more and 1,000,000 or less in termsof polystyrene can be obtained according to the method for producingcopolymers of the polar group-containing allyl monomers of the presentinvention. Such copolymers can be used in various molding methods.

Also, the method enables obtaining the copolymer with moleculardistribution (Mw/Mn) as narrow as 1.0 or more and 3.0 or less. Thenarrow molecular distribution contributes to cutting back alow-molecular-weight or high-molecular-weight content, which generallyhas a positive effect on physical properties of the polymer andfacilitates controlling the molecular distribution to achieve propertybalance as well.

The content of the monomer unit represented by formula (4) (mol%={m/(m+n)}×100) is preferably 0.1% or more and 50% or less. The contentof the monomer unit represented by formula (4) is preferably 0.5 to 15.0mol %, more preferably 1.0 to 6.0 mol % from the viewpoint of having asimilar melt viscosity and molding conditions to those of polyethylene.When there are multiple monomer units represented by formula (4), mshould be the total of each of the monomer units. As mentioned above, athird monomer unit other than monomer units represented by formulae(3-1) and (4) may be copolymerized.

In the copolymer of the present invention, a part or all of the monomerunit represented by formula (4) may be saponified. When the monomer unitrepresented by formula (4) is derived from allyl acetate, the copolymerafter saponification has a structure as follows. The monomer unit offormula (4-2) derived from allyl acetate is saponified and changes tothe monomer unit derived from allyl alcohol represented by formula(4-1). m₁+m₂=m. When all of the monomer unit represented by aresaponified, m₁ becomes 0. The ratio between m₁ and m₂ can be adjusted bythe degree of saponification. The saponification of the copolymer isconducted by a known method similar to that of saponifying poly(vinylacetate). The copolymer can be dissolved or dispersed in a solvent andtreated with acid and alkali in the presence of water and alcohol.

(In the formula, R¹⁻¹ has the same meaning as mentioned above and n, m₁and m₂ are the values to indicate the molar ratio between each of themonomer units.)

The copolymer of N-t-butoxycarbonyl-N-allylamine and ethylene and thelike can be converted to a copolymer of allylamine or allyl ammoniumsalts by hydrolysis under an acidic condition. When the copolymer ispartially saponified, it becomes a tripolymer of ethylene, allylamineand N-t-butoxycarbonyl-N-allylamine.

EXAMPLES

Hereinafter, the present invention is described in greater detail byreferring to Examples and Comparative Examples. The present invention isby no means limited thereto.

[Method for Analyzing the Polymer Structure]

The structure of the copolymers obtained in Examples was determined byvarious analysis of the NMR spectra using JNM-ECS400 manufactured byJEOL Ltd. The content of the monomer unit derived from the allylcompound represented by formula (2) and the terminal structure of thecopolymer was determined by analyzing ¹³C-NMR spectrum (90° pulse at 9.0microseconds, spectrum width: 31 kHz, relaxation time: 10 seconds,acquisition time: 10 seconds, times of accumulating FID signals: 5,000to 10,000 times) through the inverse-gated decoupling method at 120° C.using 1,2,4-trichlorobenzene (0.55 ml) as a solvent and Cr(acac)₃ (10mg) as relaxation agent.

A branched structure can be determined by analyzing ¹³C-NMR spectrum ofthe tertiary carbon atom. That is, while the chemical shift value of thecarbon atom in the branch of allyl acetate (corresponding to carbon atomd in FIG. 3) appears at 37.9 ppm, the chemical shift value of thetertiary carbon atom (carbon atom at the branch point) appears in thevicinity of 38.2 to 39 ppm when there is a branch in the polymer mainchain, thereby permitting the distinction between the two (see FIG. 3)(Reference document: Macromolecules 1999, 32, 1620-1625).

Similarly, a terminal structure can be analyzed by ¹³C-NMR or ¹H-NMRspectrum. Particularly, when the copolymer contains a terminal doublebond, peaks appears at 114 ppm and 139 ppm in ¹³C-NMR spectrum, whichcan be differentiated from the peak attributed to a saturated terminalstructure that appears in the range of 10 to 40 ppm (Reference document:Chem. Commun. 2002, 744-745).

A number average molecular weight and a weight average molecular weightwere calculated by size extrusion chromatography in which polystyrene isemployed as an internal standard substance using a high-temperature GPCapparatus, HLC-8121GPC/HT, manufactured by Tosoh Corporation, providedwith TSKgel GMHHR-H(S) HT column (two columns of 7.8 mm I.D.×30 cmarranged in series) manufactured by Tosoh Corporation (solvent:1,2-dichlorobenzene, temperature: 145° C.)

Metal complex catalyst 1 was synthesized according to the followingreaction scheme:

[Synthesis of Metal Complex Catalyst 1]

(a) Synthesis of Compound 1a

n-butyllithium (manufactured by Kanto Chemical Co., Inc., 1.65 M hexanesolution, 5.1 ml, 8.4 mmol) was added to a tetrahydrofuran (THF)solution (20 ml) of benzenesulfonic acid (manufactured by Tokyo ChemicalIndustry Co., Ltd., 662 mg, 4.2 mmol) at 0° C. under argon atmosphereand the mixture was stirred for 2.5 hours at room temperature. Aftercooling the reaction container to −78° C., chlorodicyclohexylphosphine(manufactured by Sigma-Aldrich, 885 mg, 3.8 mmol) was added thereto at−78° C. and stirred for 24 hours at room temperature. After ceasing thereaction by trifluoroacetic acid (manufactured by Tokyo ChemicalIndustry Co., Ltd., 0.5 M THF solution, 8.4 ml, 4.2 mmol), the generatedprecipitate was recovered by filtration and dried under reduced pressureto obtain phosphonium sulfonate (compound 1a). The yield was 656 mg(85).

¹H-NMR (400 MHz, CDCl₃): δ 0.98-0.27 (m, 4H), 1.30-1.58 (m, 6H),1.62-1.78 (m, 4H), 1.88 (br s, 4H), 2.28 (br s, 2H), 3.33 (br s, 2H),5.19 (br d, ¹J_(PH)=370 Hz, 1H), 7.48-7.58 (m, 2H), 7.80 (br s, 1H),8.27 (br s, 1H);

¹³C-NMR (101 MHz, CDCl₃): δ 25.0 (s), 25.6-26.2 (m), 28.8 (br), 30.3(br), 34.6 (br d, ¹J_(PC)=40 Hz), 113.4 (br d, ¹J_(PC)=87 Hz), 128.8 (d,J_(PC)=9 Hz), 130.1 (d, J_(PC)=9 Hz), 135.4 (br), 137.1 (br), 150.5(br);

³¹P-NMR (162 MHz, CDCl₃): δ 52.8 (d, ¹J_(PH)=370 Hz) (90%), 20.8 (d,¹J_(PH)=530 Hz) (10%);

Anal. calcd for C₁₈H₂₇O₃PS, C, 60.99; H, 7.68.

found: C, 60.90; H, 7.55.

(b) Synthesis of Complex 1b

A methylene chloride solution (6 ml) of (COD)PdMeCl (synthesizedaccording to “Chem., 1993, 32, 5769-5778; COD: 1,5-cyclooctadiene; 321mg; 1.2 mmol) was added to a methylene chloride solution (16 ml) of2-(dicyclohexylphosphino)benzenesulfonic acid; compound 1a) (426 mg, 1.2mmol) and diisopropylethyl amine (manufactured by Wako Chemical PureChemical Industries Ltd.; 1.1 ml, 6.0 mmol) under argon atmosphere andthe mixture was stirred for one hour at room temperature. Aftercondensing the solvent, the precipitation was removed by filtration andthe solvent was added to hexane. The generated precipitate was recoveredby filtration, washed with hexane and then dried under reduced pressureto obtain complex 1b. The yield was 656 mg (85%).

¹H-NMR (500 MHz, CDCl₃): δ 0.71 (d, ³J_(PH)=1.4 Hz, 3H, PdCH₃),1.11-1.35 (m, 8H), 1.45 (d, J=6.6 Hz, 6H, HNCH(CH₃)₂), 1.57 (d, J=6.6Hz, 6H, HNCH(CH₃)₂), 1.57 (t, J=7.3 Hz, 3H, HNCH₂CH₃), 1.60-1.70 (m,6H), 1.72-1.84 (m, 4H), 2.12-2.28 (m, 4H), 3.29 (dq, J=7.3, 5.0 Hz, 2H,HNCH₂CH₃), 3.92-4.01 (m, 2H, HNCH(CH₃)₂), 7.45 (dd, J=7.2, 7.2 Hz, 1H),7.49 (dd, J=7.6, 7.6 Hz, 1H), 7.59 (dd, J=7.3, 7.3 Hz, 1H), 8.21 (ddd,J=7.7, 3.6, 1.3 Hz, 1H), 8.87 (br, 1H, NH);

¹³C-NMR (101 MHz, CDCl₃): δ −7.3 (s, PdCH₃), 12.0 (s, HNCH₂CH₃), 17.9(s, HNCH(CH₃)₂), 19.2 (s, HNCH(CH₃)₂), 26.0 (s), 26.9-27.4 (m), 28.7(s), 29.4 (d, J_(PC)=4 Hz), 35.6 (d, ¹J_(PC)=25 Hz), 42.4 (s, HNCH₂CH₃),54.6 (s, HNCH(CH₃)₂), 125.5 (d, ¹J_(PC)=33 Hz), 128.3 (d, J_(PC)=7 Hz),128.9 (d, J_(PC)=6 Hz), 130.3 (s), 132.5 (s), 150.9 (d, ²J_(PC)=11 Hz);

³¹P-NMR (162 MHz, CDCl₃): δ 31.7;

Anal. calcd for C₂₇H₄₉ClNO₃PPdS, C, 50.62; H, 7.71; N, 2.19.

found: C, 50.49; H, 8.00, N, 2.12.

(c) Synthesis of Metal Complex Catalyst 1

A methylene chloride solution (4 ml) of complex 1b (194 mg, 0.30 mmol)was added to a methylene chloride suspension (2 ml) of potassiumcarbonate (420 mg, 3.03 mmol) and 2,6-lutidine (manufactured by TokyoChemical Industry Co., Ltd., 333 mg, 3.11 mmol) under argon atmosphereand stirred for one hour at room temperature. Solid remained afterdistilling away the solvent under reduced pressure was washed withdiethyl ether and extracted with a methylene chloride solution. Theextract was filtered through by Celite (dry diatom earth) and slowlyadded to hexane (40 ml). The generated precipitate was recovered byfiltration, washed with hexane and then dried under reduced pressure toobtain metal complex catalyst 1. The yield was 123 mg (70%).

¹H-NMR (400 MHz, CDCl₃): δ 0.32 (d, ³J_(PH)=2.3 Hz, 3H, PdCH₃),1.12-1.47 (m, 8H), 1.60-1.94 (m, 10H), 2.22-2.33 (m, 4H), 3.18 (s, 6H,CH₃ of lutidine), 7.12 (d, J=7.7 Hz, 2H), 7.47 (dd, J=7.6, 7.6 Hz, 1H),7.52 (dddd, J=7.6, 7.6, 1.4, 1.4 Hz, 1H), 7.58 (dd, J=8.1, 8.1 Hz, 1H),7.60 (dd, J=7.5, 7.5 Hz, 1H), 8.29 (ddd, 7.8, 3.9, 1.5 Hz, 1H);

¹³C-NMR (101 MHz, CDCl₃): δ−9.4 (d, ²J_(PC)=4.8 Hz, PdCH₃), 26.3 (s, CH₃of lutidine), 26.9-27.5 (m), 28.6 (s), 29.6 (d, J_(PC)=3 Hz), 35.5 (d,¹J_(PC)=26 Hz), 122.5 (s), 122.5 (s), 124.6 (d, ¹J_(PC)=35 Hz), 128.9(d, J_(PC)=7 Hz), 129.0 (d, J_(PC)=6 Hz), 130.7 (s), 132.4 (s), 138.1(s). 151.0 (d, ²J_(PC)=12 Hz), 159.0 (s);

³¹P-NMR (162 MHz, CDCl₃): δ 27.5;

Anal. calcd for C₂₆H₃₈NO₃PPdS, C, 53.65; H, 6.58; N, 2.51.

found: C, 53.51; H, 6.74; N, 2.40.

Example 1 Copolymerization of Allyl Acetate and Ethylene (Preparation ofCopolymer 1)

Methylene chloride (3.75 ml), toluene (3.75 ml) and allyl acetate (7.5ml, 7.0 g, 70 mmol) were added to a 50 ml-volume autoclave containingmetal complex catalyst 1 (58.2 g, 0.10 mmol) under argon atmosphere.After filling the autoclave with ethylene (3.0 MPa), the content of theautoclave was stirred at 80° C. for three hours. After cooling theautoclave to room temperature, methanol (about 20 ml) was added thereto.The generated copolymer was recovered by filtration, washed withmethanol and dried under reduced pressure to obtain copolymer 1. Theyield was 754 mg. The number average molecular weight and weight averagemolecular weight of the copolymer were calculated 8,100 and 16,200,respectively, by size exclusion chromatography and Mw/Mn was 2.0. Theallyl acetate content in the copolymer was determined 100:3.4 by molarratio of ethylene to allyl acetate (molar fraction of allylacetate=3.3%) by ¹³C-NMR spectrum using the inverse-gated decouplingmethod. The ¹³C-NMR signal was not observed in the chemical shift valueof the tertiary carbon atoms (δc=38.2 ppm) derived from a branch havingtwo or more carbon atoms. From the detection limit in this case, thecopolymer was found to be a linear polymer having one or less branch per1000 carbon atoms. Also, ¹³C-NMR signal was observed at 114 ppm and 139ppm, which was derived from a terminal double bond, and the copolymerwas confirmed to be a polymer containing a terminal double bond. Inaddition, in the IR spectrum shown in FIG. 4, a peak derived from acarbonyl group was observed at 1744 cm⁻¹.

The polymerization conditions and results are shown in Tables 1 and 2.

Here, the productivity and the catalyst activity were calculated by thefollowing formulae.

Productivity (g/mmol)=Yield of the obtained copolymer (g)/Molar numberof the used metal complex catalyst (mmol)

Catalyst activity (g/mmol·h)=Yield of the obtained copolymer (g)/(Molarnumber of the used metal complex catalyst (mmol)×reaction time (h))

Example 2 Copolymerization of Allyl Acetate and Ethylene (Preparation ofCopolymer 2)

Toluene (7.5 ml) and allyl acetate (7.5 ml, 7.0 g, 70 mmol) were addedto a 50 ml-volume autoclave containing metal complex catalyst 1 (58.2 g,0.10 mmol) under argon atmosphere. After filling the autoclave withethylene (3.0 MPa), the content of the autoclave was stirred at 80° C.for three hours. After cooling the autoclave to room temperature,methanol (about 20 ml) was added thereto. The generated copolymer wasrecovered by filtration, washed with methanol and dried under reducedpressure to obtain copolymer 2. The yield was 585 mg. The number averagemolecular weight and weight average molecular weight of the copolymerwere calculated 7,900 and 15,500, respectively, by size exclusionchromatography and Mw/Mn was 2.0. The allyl acetate content in thecopolymer was determined 100:4.4 by molar ratio of ethylene to allylacetate (molar fraction of allyl acetate=4.2%) by ¹³C-NMR spectrum usingthe inverse-gated decoupling method. The ¹³C-NMR signal was not observedin the chemical shift value of the tertiary carbon atoms (δc=38.2 ppm)derived from a branch having two or more carbon atoms. Also, ¹³C-NMRsignal was observed at 114 ppm and 139 ppm, which was derived from aterminal double bond, and the copolymer was confirmed to be a linearpolymer containing a terminal double bond. The polymerization conditionsand results are shown in Tables 1 and 2.

Example 3 Copolymerization of Allyl Acetate and Ethylene (Preparation ofCopolymer 3)

Metal complex catalyst 2 was synthesized in the same way as in metalcomplex catalyst 1 using 2-(dicyclopentylphosphino)benzenesulfonic acidas a starting material.

Using the obtained metal complex catalyst 2, the copolymerization ofallyl acetate and ethylene was conducted in the same way as in Example2. That is, toluene (7.5 ml) and allyl acetate (7.5 ml, 7.0 g, 70 mmol)were added to a 50 ml-volume autoclave containing metal complex catalyst2 (0.10 mmol) under argon atmosphere. After filling the autoclave withethylene (3.0 MPa), the content of the autoclave was stirred at 80° C.for three hours. After cooling the autoclave to room temperature,methanol (about 20 ml) was added thereto. The generated copolymer wasrecovered by filtration, washed with methanol and dried under reducedpressure to obtain copolymer 3. The yield was 226 mg. The number averagemolecular weight and weight average molecular weight of the copolymerwere calculated 3,400 and 5,400, respectively, by size exclusionchromatography and Mw/Mn was 1.6. The allyl acetate content in thecopolymer was determined 100:2.0 by molar ratio of ethylene to allylacetate (molar fraction of allyl acetate=2.0%) by ¹³C-NMR spectrum usingthe inverse-gated decoupling method. The ¹³C-NMR signal was not observedin the chemical shift value of the tertiary carbon atoms (δc=38.2 ppm)derived from a branch having two or more carbon atoms. Also, ¹³C-NMRsignal was observed at 114 ppm and 139 ppm, which was derived from aterminal double bond, and the copolymer was confirmed to be a linearpolymer containing a terminal double bond. The polymerization conditionsand results are shown in Tables 1 and 2.

Example 4 Copolymerization of Allyl Acetate and Ethylene (Preparation ofCopolymer 4)

Metal complex catalyst 3 was synthesized in the same way as in metalcomplex catalyst 1 using 2-(diisopropylphosphino)benzenesulfonic acid asa starting material.

Using the metal complex catalyst 3, copolymerization of allyl acetateand ethylene was conducted in the same way as in Example 2. That is,toluene (7.5 ml) and allyl acetate (7.5 ml, 7.0 g, 70 mmol) were addedto a 50 ml-volume autoclave containing metal complex catalyst 3 (0.10mmol) under argon atmosphere. After filling the autoclave with ethylene(3.0 MPa), the content of the autoclave was stirred at 80° C. for threehours. After cooling the autoclave to room temperature, methanol (about20 ml) was added thereto. The generated copolymer was recovered byfiltration, washed with methanol and dried under reduced pressure toobtain copolymer 4. The yield was 525 mg. The number average molecularweight and weight average molecular weight of the copolymer werecalculated 6,700 and 12,700, respectively, by size exclusionchromatography and Mw/Mn was 1.9. The allyl acetate content in thecopolymer was determined 100:2.7 by molar ratio of ethylene to allylacetate (molar fraction of allyl acetate=2.0%) by ¹³C-NMR spectrum usingthe inverse-gated decoupling method. The ¹³C-NMR signal was not observedin the chemical shift value of the tertiary carbon atoms (δc=38.2 ppm)derived from a branch having two or more carbon atoms. Also, ¹³C-NMRsignal was observed at 114 ppm and 139 ppm, which was derived from aterminal double bond, and the copolymer was confirmed to be a linearpolymer containing a terminal double bond. The polymerization conditionsand results are shown in Tables 1 and 2.

Comparative Example 1 Copolymerization of Allyl Acetate and Ethylene byRadical Polymerization

Copolymerization of allyl acetate and ethylene was conducted using aradical generator AIBN (2,2-azobisisobutylonitrile) in place of a metalcomplex catalyst. That is, AIBN (0.742 g, 4.52 mmol) and allyl acetate(80 ml, 74.6 g, 747 mmol) were placed into a 120 ml-volume autoclave.After filling the autoclave with ethylene so that the pressure becomes1.0 MPa, the content of the autoclave was stirred at 90° C. for twohours. Regarding the ethylene pressure during the reaction, after adecrease in pressure owing to the ethylene amount dissolved in a solvent(for about ten minutes after starting applying the ethylene pressure),no more decrease in the ethylene pressure due to the reaction wasobserved. After cooling the autoclave to room temperature, the obtainedsolution was distilled under reduced pressure to distill away unreactedally acetate to obtain 7.3 g of an oily substance. By the analysis of¹H-NMR and ¹³C-NMR of the obtained oily substance, it was found to be anoligomer in which only allyl acetate was reacted (molar fraction ofallyl acetate=100.0%) and no ethylene skeleton by ethylenecopolymerization exists. The number average molecular weight and weightaverage molecular weight of the copolymer were calculated 1,600 and2,800, respectively, by size exclusion chromatography and Mw/Mn was 1.9.The polymerization conditions and results are shown in Tables 1 and 2.

[Synthesis of Metal Complex Catalyst 4]

A methylene chloride solution of2-[bis(2-methoxyphenyl)phosphino]benzenesulfonic acid (0.46 g, 1.1 mmol)and (TMEDA)PdMe₂ (synthesized according to “Organometallics” 1989, 8,2907-2917; TMEDA=N,N,N′N′-tetramethylethylenediamine, 0.29 g, 1.1 mmol)(7 ml) was stirred under nitrogen atmosphere at room temperature for 0.5hour. Subsequently, 2,6-lutidine (1.2 g, 11.4 mmol) was added to thereaction solution and further stirred for three hours. After condensingthe solution, the precipitate was removed by the filtration using asyringe filter, and the solution was added dropwise to hexane. Thegenerated precipitate was recovered by filtration, washed witht-butylmethyl ether and hexane, and dried under reduced pressure toobtain metal complex catalyst 4. The yield was 0.46 g (64%).

¹H-NMR (400 MHz, CDCl₃): δ −0.06 (d, ³J_(PH)=1.2 Hz, 3H, PdCH₃), 3.15(s, 6H, CH₃ of lutidine), 3.61 (s, 6H, OCH₃), 6.90-6.93 (m, 2H),7.03-7.11 (m, 4H), 7.32-7.57 (m, 6H), 7.77 (br s, 2H), 8.16 (br s, 1H)

[Synthesis of Metal Complex Catalyst 5]

A methylene chloride solution of 2-(diisopropylphosphino)benzenesulfonicacid (0.96 g, 3.5 mmol) and (TMEDA)PdMe₂ (0.88 g, 1.1 mmol) (30 ml) wasstirred under nitrogen atmosphere at room temperature for 1.5 hours.After condensing the solution, the precipitate was removed by thefiltration using a syringe filter, and the solution was added dropwiseto hexane. The generated precipitate was recovered by filtration, washedwith t-butylmethyl ether and hexane, and dried under reduced pressure toobtain metal complex catalyst 5. The yield was 1.6 g (98%).

¹H-NMR (400 MHz, CDCl₃): δ 0.39 (s, 6H, PdCH₃), 1.23 (br, 24H,P[CH(CH₃)₂]₂), 2.57 (br, 2H, PC[H(CH₃)₂]₂), 2.64 (s, 12H,(CH₃)₂NCH₂CH₂N(CH₃)₂), 3.48 (s, 4H, (CH₃)₂NCH₂CH₂N(CH₃)₂), 7.48-7.55 (m,6H), 8.29 (br, 2H)

[Synthesis of Metal Complex Catalyst 6]

A dimethyl sulfoxide (dmso) solution of metal complex catalyst 5 (0.48g, 0.53 mmol) (10 ml) was stirred under nitrogen atmosphere and reducedpressure at 40° C. for ten hours. After adding methylene chloride (30ml) and water (30 ml) to the reaction solution, an organic layer and awater layer were separated using a separating funnel. After drying theorganic layer with magnesium sulfate, the solvent was distilled awaywith an evaporator. Methylene chloride (10 ml) was added to the residueto dissolve it, and the obtained solution was added dropwise to hexane(50 ml). The generated precipitate was recovered by filtration, washedwith t-butylmethyl ether and hexane, and dried under reduced pressure toobtain metal complex catalyst 6. The yield was 0.26 (52%).

¹H-NMR (400 MHz, CDCl₃): δ 0.68 (s, 3H, PdCH₃), 1.21-1.32 (m, 12H,P[CH(CH₃)₂]₂), 2.49-2.58 (m, 2H, P[CH(CH₃)₂]₂), 2.88 (s, 6H,CH₃(S═O)CH₃), 7.47-7.58 (m, 3H), 8.31-8.33 (m, 1H)

[Synthesis of Metal Complex Catalyst 7]

A methylene chloride solution of 2-(diisopropylphosphino)benzenesulfonicacid (0.33 g, 1.2 mmol) and (TMEDA)PdMe₂ (0.30 g, 1.2 mmol) (10 ml) wasstirred under nitrogen atmosphere at room temperature for 0.5 hour.Pyridine (manufactured by Wako Pure Chemical Industries, Ltd., 0.48 g,6.0 mmol) was added to the reaction solution and stirred for another onehour. After condensing the solution, the precipitate was removed by thefiltration using a syringe filter, and the solution was added dropwiseto hexane. The generated precipitate was recovered by filtration, washedwith t-butylmethyl ether and hexane, and dried under reduced pressure toobtain metal complex catalyst 7. The yield was 0.39 g (68%).

¹H-NMR (400 MHz, CDCl₃): δ 0.57 (s, 3H, PdCH₃), 1.19•1.35 (m, 12H,P[CH(CH₃)₂]₂), 2.52-2.61 (m, 2H, P[CH(CH₃)₂]₂), 7.47-7.59 (m, 5H),7.82-7.87 (m, 1H), 8.35 (br, 1H), 8.87 (br, 2H)

[Synthesis of Metal Complex Catalyst 8]

A methylene chloride solution of (2-diisopropylphosphino)benzenesulfonicacid (0.22 g, 0.81 mmol) and (TMEDA)PdMe₂ (0.21 g, 0.81 mmol) (8 ml) wasstirred under nitrogen atmosphere at room temperature for 0.5 hour.2-methylquinoline (manufactured by Tokyo Chemical Industry Co., Ltd.,1.2 g, 8.1 mmol) was added to the reaction solution and stirred foranother two hours. After condensing the solution, the precipitate wasremoved by the filtration using a syringe filter, and the solution wasadded dropwise to hexane. The generated precipitate was recovered byfiltration, washed with t-butylmethyl ether and hexane, and dried underreduced pressure to obtain metal complex catalyst 8. The yield was 0.41g (95%).

¹H-NMR (400 MHz, CDCl₃): δ 0.39 (s, 3H, PdCH₃), 1.30-1.49 (m, 12H,P[CH(CH₃)₂]₂), 2.62-2.69 (m, 2H, P[CH(CH₃)₂]₂), 3.43 (s, 3H,2-CH₃-quinoline), 7.41-7.64 (m, 5H), 7.81-7.86 (m, 2H), 8.19 (d, 1H,J=8.0 Hz), 8.30 (br, 1H), 9.58 (d, 1H, J=8.0 Hz)

[Synthesis of Metal Complex Catalyst 9]

A methylene chloride solution of(2-diisopropylphosphino-4-ethylbenzenesulfonic acid) (0.37 g, 1.2 mmol)which was synthesized in the same way as compound 1a using4-ethylbenzenesulfonic acid (manufactured by Sigma-Aldrich) as astarting material and (TMEDA)PdMe₂ (0.31 g, 1.2 mmol) (8 ml) was stirredunder nitrogen atmosphere at room temperature for 0.5 hour.Subsequently, 2,6-lutidine (1.3 g, 12.3 mmol) was added to the reactionsolution and further stirred for two hours. After condensing thesolution, the precipitate was removed by the filtration using a syringefilter, and the solution was added dropwise to hexane. The generatedprecipitate was recovered by filtration, washed with t-butylmethyl etherand hexane, and dried under reduced pressure to obtain metal complexcatalyst 9. The yield was 0.51 g (77%).

¹H-NMR (400 MHz, CDCl₃): δ 0.33 (s, 3H, PdCH₃), 1.26-1.39 (m, 15H),2.52-2.73 (m, 4H), 3.18 (s, 6H, CH₃ of lutidine), 7.12 (d, 2H, J=7.2Hz), 7.33-7.37 (m, 2H), 7.57 (t, 1H, J=7.2 Hz), 8.20 (br, 1H)

[Synthesis of Metal Complex Catalyst 10]

A THF solution of2-bis(2′,6′-dimethoxy-2-biphenyl)phosphinobenzenesulfonic acid) (0.53 g,0.87 mmol) which was synthesized in the same way as compound 1a usingbenzenesulfonic acid (manufactured by Sigma-Aldrich) as a startingmaterial and (TMEDA)PdMe₂ (0.22 g, 0.87 mmol) (12 ml) was stirred undernitrogen atmosphere at room temperature for 0.5 hour. Subsequently,2,6-lutidine (0.93 g, 8.7 mmol) was added to the reaction solution andfurther stirred for four hours. After adding t-butylmethyl ether (10 ml)to the reaction solution, the generated precipitate was recovered byfiltration, washed with t-butylmethyl ether and hexane, and dried underreduced pressure to obtain metal complex catalyst 10. The yield was 0.50g (69%).

¹H-NMR (400 MHz, CDCl₃): δ 0.16 (s, 3H, PdCH₃), 3.14 (s, 6H, CH₃ oflutidine), 3.48-3.74 (m, 12H), 6.12-8.27 (m, 21H)

Example 5 Copolymerization of Allyl Acetate and Ethylene (Preparation ofCopolymer 5)

Methylene chloride (3.75 ml), toluene (3.75 ml) and allyl acetate (7.5ml, 7.0 g, 70 mmol) were added to a 50 ml-volume autoclave containingmetal complex catalyst 4 (0.10 mmol) under argon atmosphere. Afterfilling the autoclave with ethylene (3.0 MPa), the content of theautoclave was stirred at 80° C. for three hours. After cooling theautoclave to room temperature, methanol (about 20 ml) was added thereto.The generated copolymer was recovered by filtration, washed withmethanol and dried under reduced pressure to obtain copolymer 5. Theyield was 0.29 g. The number average molecular weight and weight averagemolecular weight of the copolymer were calculated 4,000 and 7,000,respectively, by size exclusion chromatography and Mw/Mn was 1.7. Theallyl acetate content in the copolymer was determined to be 3.7% bymolar ratio by ¹³C-NMR spectrum using the inverse-gated decouplingmethod. The ¹³C-NMR signal was not observed in the chemical shift valueof the tertiary carbon atoms (δc=38.2 ppm) derived from a branch havingtwo or more carbon atoms. Also, ¹³C-NMR signal was observed at 114 ppmand 139 ppm, which was derived from a terminal double bond, and thecopolymer was confirmed to be a linear polymer containing a terminaldouble bond. The polymerization conditions and results are shown inTables 1 and 2.

Example 6 Copolymerization of Allyl Acetate and Ethylene (Preparation ofCopolymer 6)

A toluene solution (37.5 ml) of metal complex catalyst 1 (0.10 mmol) wasadded to a 120 ml-volume autoclave containing allyl acetate (37.5 ml,34.9 g, 350 mmol) under nitrogen atmosphere. After filling the autoclavewith ethylene (3.0 MPa), the content of the autoclave was stirred at 80°C. for five hours. After cooling the autoclave to room temperature, thereaction mixture was added to methanol (400 ml). The generated copolymerwas recovered by filtration, washed with methanol and dried underreduced pressure to obtain copolymer 6. The yield was 2.1 g. The numberaverage molecular weight and weight average molecular weight of thecopolymer were calculated 14,000 and 29,000, respectively, by sizeexclusion chromatography and Mw/Mn was 2.1. The allyl acetate content inthe copolymer was determined to be 3.8% by molar fraction by ¹³C-NMRspectrum using the inverse-gated decoupling method. The ¹³C-NMR signalwas not observed in the chemical shift value of the tertiary carbonatoms (δc=38.2 ppm) derived from a branch having two or more carbonatoms. Also, ¹³C-NMR signal was observed at 114 ppm and 139 ppm, whichwas derived from a terminal double bond, and the copolymer was confirmedto be a linear polymer containing a terminal double bond. Thepolymerization conditions and results are shown in Tables 1 and 2.

Examples 7 to 30 Copolymerization of Allyl Acetate and Ethylene(Preparation of Copolymers 7 to 30)

Copolymers 7 to 30 were produced in the same way as in Examples 5 and 6.The polymerization conditions and results are shown in Tables 1 and 2.

TABLE 1 Monomer of Monomer of Metal formula (1) formula (2) complexReaction Autoclave Inert Ethylene Allyl acetate catalyst tempera-Reaction Examples volume gas (MPa) (mmol) (mmol) Solvent (ml) ture (C.°) time (hr) Ex. 1 50 Ar 3.0 70 1 (0.10) CH₂Cl₂ (3.75)/ 80 3 toluene(3.75) Ex. 2 50 Ar 3.0 70 1 (0.10) toluene (7.5)  80 3 Ex. 3 50 Ar 3.070 2 (0.10) toluene (7.5)  80 3 Ex. 4 50 Ar 3.0 70 3 (0.10) toluene(7.5)  80 3 Comparative 120 N₂ 1.0 747 AIBN (4.5) None 90 2 Ex. 1 Ex. 550 Ar 3.0 70 4 (0.10) CH₂Cl₂ (3.75)/ 80 3 toluene (3.75) Ex. 6 120 N₂3.0 350 1 (0.10) toluene (37.5) 80 5 Ex. 7 120 N₂ 3.0 350 1 (0.010)toluene (37.5) 80 5 Ex. 8 120 N₂ 3.0 350 3 (0.10) toluene (37.5) 80 5Ex. 9 120 N₂ 3.0 350 3 (0.050) toluene (37.5) 80 5 Ex. 10 120 N₂ 4.0 3501 (0.050) toluene (37.5) 80 5 Ex. 11 120 N₂ 2.0 350 1 (0.050) toluene(37.5) 80 5 Ex. 12 120 N₂ 1.0 350 1 (0.50) toluene (37.5) 80 5 Ex. 13120 N₂ 3.0 350 1 (0.050) toluene (37.5) 120 5 Ex. 14 120 N₂ 3.0 350 1(0.050) toluene (37.5) 150 5 Ex. 15 50 Ar 3.0 70.0 1 (0.10) o-dichloro-80 3 benzene (7.5) Ex. 16 120 N₂ 3.0 70.0 3 (0.050) toluene (67.5) 80 5Ex. 17 120 N₂ 3.0 700 1 (0.050) None 80 5 Ex. 18 120 N₂ 4.0 700 1(0.050) None 80 5 Ex. 19 120 N₂ 4.0 700 3 (0.050) None 80 5 Ex. 20 120N₂ 3.0 350 3 (0.050) toluene (37.5) 80 26 Ex. 21 120 N₂ 3.0 350 5(0.025) toluene (37.5) 80 5 Ex. 22 120 N₂ 3.0 350 6 (0.10) toluene(37.5) 80 5 Ex. 23 120 N₂ 3.0 350 6 (0.050) toluene (37.5) 80 5 Ex. 24120 N₂ 3.0 350 6 (0.010) toluene (37.5) 80 5 Ex. 25 120 N₂ 3.0 350 7(0.050) toluene (37.5) 80 5 Ex. 26 120 N₂ 3.0 350 7 (0.010) toluene(37.5) 80 5 Ex. 27 120 N₂ 3.0 350 8 (0.050) toluene (37.5) 80 5 Ex. 28120 N₂ 3.0 350 8 (0.010) toluene (37.5) 80 5 Ex. 29 120 N₂ 3.0 350 9(0.050) toluene (37.5) 80 5 Ex. 30 120 N₂ 3.0 350 10 (0.050) toluene(37.5) 80 5 Comparative 120 N₂ 3.0 None 1 (0.050) toluene (75)   80 1Ex. 2 Comparative — — — — With — — — Ex. 3 organic aluminum Ex. 31 50 Ar3.0 70 in situ CH₂Cl₂ (3.75)/ 80 15 toluene (3.75) Ex. 32 120 N₂ 3.0 3483 (0.010) toluene (37.5) 80 5 Ex. 33 120 N₂ 3.0 348 3 (0.010) toluene(37.5) 80 25 Ex. 34 120 N₂ 3.0 348 3 (0.010) toluene (37.5) 80 50 Ex. 35120 N₂ 3.0 348 3 (0.010) toluene (37.5) 80 100

TABLE 2 Co- Catalyst Molecular weight polymer Polymer ProductivityActivity Mn Mw No. yield (g) (g/mmol) (g/mmol · h) (g/mol) (g/mol) Mw/MnA* B* C* Ex. 1 1 0.75 7.5 2.5 8100 16200 2.0 3.3 Not exist Exist Ex. 2 20.59 5.9 2.0 7900 15500 2.0 4.2 Not exist Exist Ex. 3 3 0.23 2.3 0.773400 5400 1.6 2.0 Not exist Exist Ex. 4 4 0.53 5.3 1.8 6700 12700 1.92.6 Not exist Exist Comparative Comparative 1 7.3 1.6 0.81 1600 2800 1.8100.0 — — Ex. 1 Ex. 5 5 0.29 2.9 0.97 4000 7000 1.7 3.7 Not exist ExistEx. 6 6 2.1 20.5 4.1 14000 29000 2.1 3.8 Not exist Exist Ex. 7 7 0.5454.0 10.9 15000 32000 2.1 3.3 Not exist Exist Ex. 8 8 3.0 30.4 6.1 1100026000 2.4 4.0 Not exist Exist Ex. 9 9 2.3 45.7 9.1 11000 26000 2.4 3.9Not exist Exist Ex. 10 10 2.7 53.1 10.6 16000 34000 2.1 2.4 Not existExist Ex. 11 11 0.57 11.3 2.3 10000 21000 2.1 5.7 Not exist Exist Ex. 1212 0.22 0.44 0.09 4000 6000 1.7 11.7 Not exist Exist Ex. 13 13 1.6 31.46.3 7000 15000 2.1 6.0 Not exist Exist Ex. 14 14 0.64 12.8 2.6 600013000 2.2 5.8 Not exist Exist Ex. 15 15 1.1 10.8 3.6 9000 21000 2.4 3.9Not exist Exist Ex. 16 16 3.6 72.9 14.6 16000 42000 2.6 1.0 Not existExist Ex. 17 17 1.1 21.3 4.3 8000 17000 2.1 8.2 Not exist Exist Ex. 1818 2.0 39.9 8.0 10000 24000 2.4 5.7 Not exist Exist Ex. 19 19 3.1 62.212.4 9000 23000 2.5 4.4 Not exist Exist Ex. 20 20 5.6 111.8 4.3 1100025000 2.3 4.4 Not exist Exist Ex. 21 21 0.30 6.0 1.2 8000 16000 2.1 3.2Not exist Exist Ex. 22 22 3.7 37.3 7.5 8000 16000 2.1 3.2 Not existExist Ex. 23 23 1.9 38.2 7.6 9000 21000 2.3 4.0 Not exist Exist Ex. 2424 0.82 81.6 16.3 11000 25000 2.3 3.6 Not exist Exist Ex. 25 25 0.39 7.81.6 8000 17000 2.2 3.5 Not exist Exist Ex. 26 26 0.29 29.4 5.9 1200026000 2.2 3.1 Not exist Exist Ex. 27 27 0.62 12.4 2.5 9000 19000 2.1 3.1Not exist Exist Ex. 28 28 0.42 42.0 8.4 11000 24000 2.2 3.2 Not existExist Ex. 29 29 0.47 9.4 1.9 13000 29000 2.2 3.0 Not exist Exist Ex. 3030 1.7 34.0 6.8 37000 85000 2.3 1.3 Not exist Exist ComparativeComparative 2 8.3 166.0 166.0 30000 70000 2.3 0.0 — — Ex. 2 ComparativeComparative 3 — — — — — — — — Not exist Ex. 3 Ex. 31 31 1.7 17 1.1 40009000 2.3 2.7 Not exist Exist Ex. 32 32 0.89 89 17.8 13000 29000 2.2 3.3Not exist Exist Ex. 33 33 2.1 210 8.4 12000 28000 2.3 4.0 Not existExist Ex. 34 34 3.7 370 7.4 11000 25000 2.3 3.8 Not exist Exist Ex. 3535 6.2 620 6.2 11000 25000 2.3 3.9 Not exist Exist Ex. 36 36 0.86 — —12000 26000 2.0 3.2 Not exist Exist Ex. 37 37 2.8 — — 11000 26000 2.43.8 Not exist Exist A*: Molar fraction of the allyl compound monomerunits (mol %) B*: Presence or absence of a branch having two or morecarbon atoms (δc = 38.2 ppm) C*: Presence or absence of a terminaldouble bond (δc = 114 ppm, 139 ppm)

Comparative Example 2 Ethylene Homopolymerization

Ethylene homopolymerization was conducted using metal complexcatalyst 1. That is, a toluene solution (75 ml) of metal complexcatalyst 1 (0.050 mmol) was added to a 120 ml-volume autoclave undernitrogen atmosphere. After filling the autoclave with ethylene (3.0MPa), the content of the autoclave was stirred at 80° C. for one hour.After cooling the autoclave to room temperature, the reaction mixturewas added to methanol (400 ml). The generated copolymer was recovered byfiltration, washed with methanol and dried under reduced pressure. Theyield was 8.3 g. The number average molecular weight and weight averagemolecular weight of the copolymer were calculated 30,000 and 70,000,respectively, by size exclusion chromatography and Mw/Mn was 2.1.

Comparative Example 3 The Case where Organic Aluminum was Used

When polar group-containing monomers are (co)polymerized using an earlytransition metal complex, organic aluminum is used in an amount that isequal to or more than the polar group-containing monomers. In this case,it has been reported in a publication that the polymer chain transfersto aluminum atoms, which terminates the polymerization reaction, andtherefore a terminal double bond is not observed in the polymer(Macromolecules 2004, 37, 5145).

Example 31 Copolymerization of Ally Acetate and Ethylene (In-SituPreparation of Copolymer 31)

Methylene chloride (3.75 ml), toluene (3.75 ml) and allyl acetate (7.5ml, 7.0 g, 70 mmol) were added to a 50 ml-volume autoclave containing2-(diisopropylphosphino)benzenesulfonic acid (0.12 mmol) andPd₂(DBA)₃.CHCl₃ (DBA: dibenzylideneacetone, 0.10 mmol) under argonatmosphere. After filling the autoclave with ethylene (3.0 MPa), thecontent of the autoclave was stirred at 80° C. for 15 hours. Aftercooling the autoclave to room temperature, methanol (about 20 ml) wasadded thereto. The generated precipitate was recovered by filtration,washed with methanol and dried under reduced pressure to obtaincopolymer 31. The yield was 1.7 g. The number average molecular weightand weight average molecular weight of the copolymer were calculated4,000 and 9,000, respectively, by size exclusion chromatography andMw/Mn was 2.7. The allyl acetate content in the copolymer was determinedto be 2.7% by molar fraction by ¹³C-NMR spectrum using the inverse-gateddecoupling method. The ¹³C-NMR signal was not observed in the chemicalshift value of the tertiary carbon atoms (δc=38.2 ppm) derived from abranch having two or more carbon atoms. Also, ¹³C-NMR signal wasobserved at 114 ppm and 139 ppm, which was derived from a terminaldouble bond, and the copolymer was confirmed to be a linear polymercontaining a terminal double bond.

Example 32 Copolymerization of Allyl Acetate and Ethylene (Preparationof Copolymer 32)

A toluene solution (37.5 ml) of metal complex catalyst 3 (0.010 mmol)was added to a 120 ml-volume autoclave containing allyl acetate (37.5ml, 34.9 g, 348 mmol) under nitrogen atmosphere. After filling theautoclave with ethylene (3.0 MPa), the content of the autoclave wasstirred at 80° C. for five hours. After cooling the autoclave to roomtemperature, the reaction mixture was added to methanol (about 400 ml).The generated precipitate was recovered by filtration, washed withmethanol and dried under reduced pressure to obtain copolymer 32. Theyield was 0.89 g. The number average molecular weight and weight averagemolecular weight of the copolymer were calculated 13,000 and 29,000,respectively, by size exclusion chromatography and Mw/Mn was 2.2. Theallyl acetate content in the copolymer was determined to be 3.3% bymolar fraction by ¹³C-NMR spectrum using the inverse-gated decouplingmethod. The ¹³C-NMR signal was not observed in the chemical shift valueof the tertiary carbon atoms (δc=38.2 ppm) derived from a branch havingtwo or more carbon atoms. Also, ¹³C-NMR signal was observed at 114 ppmand 139 ppm, which was derived from a terminal double bond, and thecopolymer was confirmed to be a linear polymer containing a terminaldouble bond.

Examples 33 to 35 Copolymerization of Allyl Acetate and Ethylene(Preparation of Copolymers 33 to 35)

Copolymers 33 to 35 were obtained in the same manner as in Example 32except for setting the reaction time to 25 hours, 50 hours and 100hours, respectively. The polymerization conditions and results are shownin Tables 1 and 2.

The polymer productivity per catalyst with respect to the polymerizationtime in Examples 32 to 35 is shown as a graph in FIG. 16. It can be seenthat the present polymerization catalyst system shows very little lossof catalyst activity and the polymer yield increases with thepolymerization time. This greatly differs from the phenomenon incopolymerization of ethylene and vinyl acetate that the polymerizationactivity decreases with the polymerization time and the polymerproductivity hits a peak (e.g.: see “J. Am. Chem. Soc.”, 2009, 131,14606, Supporting Information S10) and shows that the present inventionis an effective technology for promoting industrialization.

Example 36 Saponification Reaction of the Allyl Acetate and EthyleneCopolymer (Preparation of Copolymer 36)

A toluene (115 ml) and ethanol (35 ml) suspension of the allyl acetateand ethylene copolymer obtained in Example 6 (1.0 g) and potassiumhydroxide (0.056 g, 1.1 mmol) was stirred under nitrogen atmosphere at80° C. for six hours. After being cooled to room temperature, thereaction solution was added to methanol (500 ml). The generatedprecipitate was recovered by filtration, washed with methanol and thendried under reduced pressure to obtain copolymer 36. The yield was 0.86g. The analysis of the obtained powder by ¹³C-NMR and IR spectra showedthat the ester groups present in the allyl acetate and ethylenecopolymer were completely converted to hydroxyl groups and the powder isa copolymer of allyl alcohol and ethylene. The IR spectrum is shown inFIG. 5. The allyl alcohol content was determined to be 3.2% by molarfraction by ¹³C-NMR. The ¹³C-NMR signal was not observed in the chemicalshift value of the tertiary carbon atoms (δc=38.2 ppm) derived from abranch having two or more carbon atoms. Also, ¹³C-NMR signal wasobserved at 114 ppm and 139 ppm, which was derived from a terminaldouble bond, and the copolymer was confirmed to be a polymer containinga terminal double bond. In addition, the number average molecular weightand weight average molecular weight of the copolymer were calculated12,000 and 26,000, respectively, by size exclusion chromatography andMw/Mn was 2.2.

Example 37 Partial Saponification Reaction of the Allyl Acetate andEthylene Copolymer (Preparation of Copolymer 37)

A toluene (75 ml) and ethanol (5 ml) suspension of the allyl acetate andethylene copolymer obtained in Example 20 (3.0 g) and potassiumhydroxide (0.0023 g, 0.042 mmol) was stirred at 80° C. for 30 minutesunder nitrogen atmosphere. After being cooled to room temperature, thereaction solution was added to methanol (500 ml). The generatedprecipitate was recovered by filtration, washed with methanol and thendried under reduced pressure to obtain copolymer 37. The yield was 2.8g. The analysis of ¹³C-NMR of the obtained powder showed that 2.0% ofallyl acetate units and 1.8% of allyl alcohol units by molar fractionwere present in the powder. The ¹³C-NMR signal was not observed in thechemical shift value of the tertiary carbon atoms (δc=38.2 ppm) derivedfrom a branch having two or more carbon atoms. Also, ¹³C-NMR signal wasobserved at 114 ppm and 139 ppm, which was derived from a terminaldouble bond, and the copolymer was confirmed to be a linear polymercontaining a terminal double bond. In addition, the number averagemolecular weight and weight average molecular weight of the copolymerwere calculated 11,000 and 26,000, respectively, by size exclusionchromatography and Mw/Mn was 2.4.

Example 38 Copolymerization of Allyl Alcohol and Ethylene (Preparationof Copolymer 38)

A toluene solution (60 ml) of metal complex catalyst 1 (0.15 mmol) wasadded to a 120 ml-volume autoclave containing allyl alcohol (15 ml, 12.8g, 219.8 mmol) under nitrogen atmosphere. After filling the autoclavewith ethylene (4.0 MPa), the content of autoclave was stirred at 80° C.for seven hours. After being cooled to room temperature, the reactionsolution was added to methanol (400 ml). The generated copolymer wasrecovered by filtration, washed with methanol and then dried underreduced pressure to obtain copolymer 38. The yield was 0.12 g. Thenumber average molecular weight and weight average molecular weight ofthe copolymer were calculated 2,000 and 3,400, respectively, by sizeexclusion chromatography and Mw/Mn was 1.7. The allyl acetate content inthe copolymer was determined to be 2.7% by molar fraction by ¹³C-NMRspectrum using the inverse-gated decoupling method.

Examples 39 to 40 Copolymerization of Allyl Alcohol and Ethylene(Preparation of Copolymers 39 and 40)

Copolymers 39 and 40 were produced in the same manner as in Example 38except for setting the conditions shown in Table 3. The results areshown in Table 4.

Example 41 Copolymerization of Allyl Chloride and Ethylene (Preparationof Copolymer 41)

Toluene (12 ml) and allyl chloride (3 ml, 2.8 g, 36.8 mmol) were addedunder argon atmosphere to a 50 ml-volume autoclave containing metalcomplex catalyst 1 (0.10 mmol). After filling the autoclave withethylene (3.0 MPa), the content of autoclave was stirred at 80° C. for15 hours. After being cooled to room temperature, methanol (30 ml) wasadded to the autoclave. The generated copolymer was recovered byfiltration, washed with methanol and then dried under reduced pressureto obtain copolymer 41. The yield was 0.41 g. The number averagemolecular weight and weight average molecular weight of the copolymerwere calculated 10,000 and 19,000, respectively, by size exclusionchromatography and Mw/Mn was 1.9. The allyl chloride content in thecopolymer was determined to be 1.0% by molar fraction by ¹³C-NMRspectrum using the inverse-gated decoupling method. The ¹³C-NMR signalwas not observed in the chemical shift value of the tertiary carbonatoms (δc=38.2 ppm) derived from a branch having two or more carbonatoms. Also, ¹³C-NMR signal was observed at 114 ppm and 139 ppm, whichwas derived from a terminal double bond, and the copolymer was confirmedto be a linear polymer containing a terminal double bond.

Examples 42 to 43 Copolymerization of Allyl Chloride and Ethylene(Preparation of Copolymers 42 and 43)

Copolymers 42 and 43 were produced in the same manner as in Example 41except for setting the conditions shown in Table 3. The results areshown in Table 4.

Example 44 Copolymerization of Allyl Bromide and Ethylene (Preparationof Copolymer 44)

Toluene (12 ml) and allyl bromide (3 ml, 4.3 g, 35.5 mmol) were addedunder argon atmosphere to a 50 ml-volume autoclave containing metalcomplex catalyst 1 (0.10 mmol). After filling the autoclave withethylene (3.0 MPa), the content of autoclave was stirred at 80° C. for15 hours. After being cooled to room temperature, methanol (30 ml) wasadded to the autoclave. The generated copolymer was recovered byfiltration, washed with methanol and then dried under reduced pressureto obtain copolymer 44. The yield was 0.34 g. The number averagemolecular weight and weight average molecular weight of the copolymerwere calculated 8,000 and 15,000, respectively, by size exclusionchromatography and Mw/Mn was 1.9. The allyl chloride content in thecopolymer was determined to be 0.71% by molar fraction by ¹³C-NMRspectrum using the inverse-gated decoupling method. The ¹³C-NMR signalwas not observed in the chemical shift value of the tertiary carbonatoms (δc=38.2 ppm) derived from a branch having two or more carbonatoms. Also, ¹³C-NMR signal was observed at 114 ppm and 139 ppm, whichwas derived from a terminal double bond, and the copolymer was confirmedto be a linear polymer containing a terminal double bond.

Example 45 Copolymerization of Allyl Bromide and Ethylene (Preparationof Copolymer 45)

Copolymer 45 was produced in the same manner as in Example 44 except forsetting the conditions shown in Table 3. The results are shown in Table4.

Example 46 Copolymerization of N-allylaniline and Ethylene (Preparationof Copolymer 46)

Toluene (12 ml) and N-allylaniline (3 ml, 2.9 g, 22.1 mmol) were addedunder argon atmosphere to a 50 ml-volume autoclave containing metalcomplex catalyst 1 (0.10 mmol). After filling the autoclave withethylene (5.0 MPa), the content of autoclave was stirred at 120° C. for15 hours. After being cooled to room temperature, methanol (30 ml) wasadded to the autoclave. The generated copolymer was recovered byfiltration, washed with methanol and then dried under reduced pressureto obtain copolymer 46. The yield was 0.13 g. The ¹³C-NMR signal was notobserved in the chemical shift value of the tertiary carbon atoms(δc=38.2 ppm) derived from a branch having two or more carbon atoms.Also, ¹³C-NMR signal was observed at 114 ppm and 139 ppm, which wasderived from a terminal double bond, and the copolymer was confirmed tobe a linear polymer containing a terminal double bond. The numberaverage molecular weight and weight average molecular weight of thecopolymer were calculated 1,500 and 3,100, respectively, by sizeexclusion chromatography and Mw/Mn was 2.1.

Example 47 Copolymerization of N-allylaniline and Ethylene (Preparationof Copolymer 47)

Copolymer 47 was produced in the same manner as in Example 46 exceptthat the conditions are set as shown in Table 3. The results are shownin Table 4. The number average molecular weight and weight averagemolecular weight of the copolymer were calculated 2,100 and 3,200,respectively, by size exclusion chromatography and Mw/Mn was 1.5.

Example 48 Copolymerization of N-t-butoxycarbonyl-N-allylamine andEthylene (Preparation of Copolymer 48)

Toluene (15 ml) and N-t-butoxycarbonyl-N-allylamine (2.4 g, 15.0 mmol)were added under argon atmosphere to a 50 ml-volume autoclave containingmetal complex catalyst 1 (0.10 mmol). After filling the autoclave withethylene (3.0 MPa), the content of autoclave was stirred at 80° C. forthree hours. After being cooled to room temperature, methanol (30 ml)was added to the autoclave. The generated copolymer was recovered byfiltration, washed with methanol and then dried under reduced pressureto obtain copolymer 48. The yield was 1.9 g. The number averagemolecular weight and weight average molecular weight of the copolymerwere calculated 5,200 and 12,200, respectively, by size exclusionchromatography and Mw/Mn was 2.4. The N-t-butoxycarbonyl-N-allylaminecontent in the copolymer was determined to be 3.7% by molar fraction by¹³C-NMR spectrum using the inverse-gated decoupling method.

Example 49 Hydrolysis Reaction of N-t-butoxycarbonyl-N-allylamine andEthylene (Preparation of Copolymer 49)

Toluene (40 ml), ethyl alcohol (12 ml) and 35% hydrochloric acid (20 ml)were added under nitrogen atmosphere to a 100 ml-volume eggplant flaskcontaining the copolymer of N-t-butoxycarbonyl-N-allylamine and ethyleneobtained in Example 48 (0.302 g), and stirred at 78° C. for three hours.After being cooled to room temperature, the solution was neutralized byadding sodium carbonate. After being washed with water four times, thesolution was dried under reduced pressure to obtain copolymer 49. Theyield was 0.237 g. The allylamine content in the copolymer wasdetermined to be 2.0% by molar fraction by ¹³C-NMR spectrum using theinverse-gated decoupling method. The number average molecular weight andweight average molecular weight of the copolymer were calculated 2,600and 4,700, respectively, by size exclusion chromatography and Mw/Mn was1.8. The ¹³C-NMR signal was not observed in the chemical shift value ofthe tertiary carbon atoms (δc=38.2 ppm) derived from a branch having twoor more carbon atoms.

TABLE 3 Monomer of Monomer of Metal formula (1) formula (2) complexReaction Autoclave Inert Ethylene Type * catalyst tempera- ReactionExamples volume gas (MPa) (mmol) (mmol) Solvent (ml) ture (C. °) time(hr) Ex. 38 120 N₂ 4.0  AAL (219.8) 1 (0.15) toluene (60) 80 7 Ex. 39 50Ar 4.0 AAL (44.0) 3 (0.15) toluene (12) 80 7 Ex. 40 50 Ar 4.0 AAL (44.0)1 (0.10) toluene (12) 80 48 Ex. 41 50 Ar 3.0 AL-CL (36.8) 1 (0.10)toluene (12) 80 15 Ex. 42 50 Ar 3.0 AL-CL (36.8) 3 (0.15) toluene (12)90 15 Ex. 43 50 Ar 3.0 AL-CL (36.8) 1 (0.10) toluene (12) 80 3 Ex. 44 50Ar 3.0 AL-Br (35.5) 1 (0.10) toluene (12) 80 15 Ex. 45 50 Ar 3.0 AL-Br(35.5) 1 (0.10) toluene (12) 80 3 Ex. 46 50 Ar 5.0 AL-ANL (22.1) 1(0.10) toluene (12) 120 15 Ex. 47 50 Ar 5.0 AL-ANL (22.1) 1 (0.10)toluene (12) 120 24 Ex. 48 50 Ar 3.0 AL-Boc (15.0) 1 (0.10) toluene (15)80 3 * AAL: allyl alcohol AL-CL: allyl chloride AL-Br: allyl bromideAL-ANL: N-allylaniline AL-Boc: N-t-butoxycarbonyl-N-allylamine

TABLE 4 Co- Catalyst Molecular weight polymer Polymer ProductivityActivity Mn Mw No. yield (g) (g/mmol) (g/mmol · h) (g/mol) (g/mol) Mw/MnA* B* C* Ex. 38 38 0.12 0.80 0.070 2000 3400 1.7 2.7 Not exist Exist Ex.39 39 0.017 0.11 0.020 — — — 3.0 Not exist Exist Ex. 40 40 0.19 1.90.040 1100 2000 1.8 5.5 Not exist Exist Ex. 41 41 0.41 4.1 0.27 1000019000 1.9 1.0 Not exist Exist Ex. 42 42 0.88 5.9 0.39 10000 18000 1.80.87 Not exist Exist Ex. 43 43 0.47 4.7 1.6 10900 20400 1.9 0.90 Notexist Exist Ex. 44 44 0.34 3.4 0.22 8000 15000 1.9 0.71 Not exist ExistEx. 45 45 0.27 2.7 0.90 6500 11300 1.7 1.0 Not exist Exist Ex. 46 460.13 1.3 0.087 1600 3100 2.1 — Not exist Exist Ex. 47 47 0.21 2.1 0.0882100 3200 1.5 — Not exist Exist Ex. 48 48 1.9 19 6.3 5200 12200 2.4 3.7Not exist Exist Ex. 49 49 0.24 — — 2600 4700 1.8 2.0 Not exist Exist A*:Molar fraction of the allyl compound monomer units (mol %) B*: Presenceor absence of a branch having two or more carbon atoms (δc = 38.2 ppm)C*: Presence or absence of a terminal double bond (δc = 114 ppm, 139ppm)

What is claimed is:
 1. A copolymer of polar group-containing allylmonomers, which is a copolymer containing only the monomer unitsrepresented by formulae (3-1) and (4)

(in the formulae, R¹⁻¹ represents a hydrogen atom or methyl group; R²represents —OH, —OCOR³ (R³ represents hydrocarbon group having 1 to 5carbon atoms), —N(R⁴)₂ (R⁴ represents a hydrogen atom, hydrocarbon grouphaving 1 to 5 carbon atoms, aromatic residue having 6 to 18 carbon atomsor —COOR¹⁰ (R¹⁰ represents hydrocarbon group having 1 to 10 carbon atomsor aromatic residue having 6 to 10 carbon atoms) and two R⁴s may be thesame or different from each other) or a halogen atom; and n and m are avalue representing the molar ratio of each of the monomer units); (A)the main chain has one or less branch, which has two or more carbonatoms, per 1000 carbon atoms which constitute the main chain; and (B)the main chain has a carbon-to-carbon double bond at least at one end ofthe main chain.
 2. The copolymer of polar group-containing allylmonomers as claimed in claim 1 which further has a structure that: (C)the number average molecular weight in terms of polystyrene (Mn) is1,000 or more and 1,000,000 or less; (D) the molecular weightdistribution (Mw/Mn) is 1.0 or more and 3.0 or less; and (E) n and mrepresenting the molar ratio of the monomer units represented byformulae (3-1) and (4) satisfy the following formula:0.1≦{m/(m+n)}×100≦50.
 3. The copolymer of polar group-containing allylmonomers as claimed in claim 1, which contains monomer units representedby formulae (3-1), (4-1) and (4-2)

(in the formula, R¹⁻¹ has the same meaning as described above; and n, m₁and m₂ represent the molar ratio of each of the monomer units).
 4. Thecopolymer of polar group-containing allyl monomers as claimed in claim1, wherein R¹⁻¹ in formula (3-1) is a hydrogen atom.
 5. The copolymer ofpolar group-containing allyl monomers as claimed in claim 1, wherein themonomer unit represented by formula (4) is derived from at least oneallyl compound selected from allyl acetate, allyl chloride, allylbromide, allyl amine, N-allylaniline andN-t-butoxycarbonyl-N-allylamine.
 6. The copolymer of polargroup-containing allyl monomers as claimed in claim 1, wherein R¹⁻¹ informula (3-1) is a hydrogen atom and the monomer unit represented byformula (4) is derived from at least one allyl compound selected fromallyl acetate, allyl chloride, allyl bromide, allyl amine,N-allylaniline and N-t-butoxycarbonyl-N-allylamine.
 7. The copolymer ofpolar group-containing allyl monomers as claimed in claim 2, whichcontains monomer units represented by formulae (3-1), (4-1) and (4-2)

(in the formula, R¹⁻¹ has the same meaning as described above; and n, m₁and m₂ represent the molar ratio of each of the monomer units).